SYNTHESIS AND CHARACTERIZATION OF NOVEL GROUP 13 TRIDECAMERIC INORGANIC NANOCLUSTERS by JASON TREVOR GATLIN A DISSERTATION Presented to the Department of Chemistry and the Graduate School of the University of Oregon in partial fulfillment of the requirements for the degree of Doctor ofPhilosophy December 2007 11 "Synthesis and Characterization of Novel Group 13 Tridecameric Inorganic Nanoc1usters," a dissertation prepared by Jason Trevor Gatlin in partial fulfillment of the requirements for the Doctor of Philosophy degree in the Department of Chemistry. This dissertation has been approved and accepted by: Prot. Ur. Michael M. Haley, Chair o~xamining Committee /20/2007 Date / / Committee in Charge: Prof. Dr. Michael M. Haley, Chair Prof. Dr. Darren W. Johnson Prof. Dr. Kenneth M. Doxsee Prof. Dr. J. Andrew Berglund Prof. Dr. Scott D. Bridgham Accepted by: Dean of the Graduate School iii © 2007 Jason Trevor Gatlin iv An Abstract of the Dissertation of Jason Trevor Gatlin for the degree of Doctor of Philosophy in the Department of Chemistry to be taken December 2007 Title: SYNTHESIS AND CHARACTERIZATION OF NOVEL GROUP 13 TRIDECAMERIC INORGANIC NANOCLUSTERS. Approved: ---=------:---=-----=:---_--=-=:--=---::-- _ Prof. Dr. Darren W. Johnson Tridecameric inorganic hydroxo/aquo nanoclusters comprise a very small fraction of compounds under the large and varied umbrella of inorganic clusters. The Anderson­ Evans cluster is a subset of these larger polymetallic tridecameric clusters. A novel synthesis ofM13 nanoclusters containing the Anderson-Evans cluster as cores has been discovered. This synthesis proceeds with the aid of a key organic reagent, which reacts with the nitrate counter anions of the starting material removing them from the solution. This forces the formation of a higher nuclearity species. Research continues to focus on the generality of the reaction as it applies to both inorganic and organic synthesis, as well as on extensive characterization of the novel clusters by a variety ofanalytical methods. These nanoclusters have proven to be useful as single-source precursors for the preparation of thin film oxides due to their high purity and crystallinity. v Chapter I is a literature review of Anderson-Evans clusters in the context of how they comprise the core substructure in the reported tridecameric nanoclusters. Attention is also given to the numerous clusters or complexes that are absent from this series. Chapter II chronicles the discovery and synthesis of [Ga13(~3-0H)6(~Z­ OH)18(HzO)Z4](N03)15, a nanocluster previously thought to be unstable. Chapter III describes the modification of the reaction to prepare other tridecameric inorganic nanoclusters with increases in yield and purity. Chapter IV reports the isolation of a series of new heterometallic tridecameric nanoclusters and a potential predictive strategy for tuning the metal ratios in the crystalline products. Chapter IV also highlights the application of the nanoclusters as precursors to thin film oxides. Initial characterization oftridecameric inorganic nanoclusters using powder and single crystal XRD, NMR, ToF­ SIMS, EPMA and SEM instrumentation is explained in Chapter V. Finally, Chapter VI is a summary and a report of the current standing of a different project aimed at developing a template-assisted self-assembly of organic nanocages using two different ligand classes that were explored. This dissertation includes previously published and co-authored material. vi CURRICULUM VITAE NAME OF AUTHOR: Jason Trevor Gatlin PLACE OF BIRTH: Lexington, KY DATE OF BIRTH: December 21 st, 1976 GRADUATE AND UNDERGRADUATE SCHOOLS ATTENDED: University of Oregon, Eugene OR Colby College, Waterville ME DEGREES AWARDED: Doctor ofPhilosophy, 2007, University of Oregon Master of Science, 2003, University of Oregon Bachelor of Arts, 2000 Chemisty-Biochemisty, Colby College AREAS OF SPECIAL INTEREST: Supramolecular Chemistry Single Crystal XRD Organic synthesis PROFESSIONAL EXPERIENCE: Ph.D. Summer Intern, Invitrogen. June 2007 - September 2007 Graduate Research Assistant, University of Oregon, July 2002 - December 2007 Research Assistant - Encoding Specialist, Harvard Institute of Chemistry and Cell Biology, June 2000 - June 2002 Research Assistant - Summer Intern, Harvard Institute of Chemistry and Cell Biology, May 1999 -August 1999 vii Undergraduate Research Assistant, Colby College, February 1999 - May 2000 Research Intern, Biogen Inc., January 1999 PUBLICAnONS: Gatlin, 1. T.; Mensinger, Z. L.; Zakharov, L. N.; MacInnes, D.; Johnson, D. W. "Facile Synthesis of Aluminum13 Keggin-like Nanoc1uster." Inorg. Chern. manuscript accepted. Rather, E.; Gatlin, J. T.; Nixon, P. G.; Tsukamoto, T.; Kravtsov, V.; Johnson, D. W. "A Simple Organic Reaction Mediates the Crystallization of the Inorganic Nanoc1uster [Ga13(J!3-0H)6(J!2-0H)18(H20b](N03)15." J. Am. Chern. Soc. 2005, 127,3242. viii ACKNOWLEDGMENTS Support from the ARL-ONAMI Nanoarchitectures for Enhanced Performance Center and the University ofOregon is gratefully acknowledged. The purchase of the x­ ray diffractometer was made possible by a grant from the National Science Foundation (CHE-0234965). I am grateful to my committee for their continued support and helpful discussions. I am grateful to my advisor - Prof. Dr. Darren W. Johnson - for his support and the freedom to explore new chemistry. I am grateful to my reviews: Julie Larios, Melanie A. Pitt, and Dr. Nathan Lien. I am grateful to my lab mates for their help throught this research. I am very grateful to my parents, Larry and Carol Gatlin, for this support and belief. Most of all I am extremely grateful for all the support and patience from my wife Mary C. Gatlin. IX To Mary C. Gatlin and Jackson T. Gatlin x TABLE OF CONTENTS Chapter Page I. ANDERSON AND ANDERSON-CORED TRIDECAMERIC INORGANIC NANOCLUSTERS.................................................................................................... 1 Section 1 Background................................................................................ 1 Section 2 Searches and Criteria 9 Section 3 Ligands and Stability.................................................................. 15 Section 4 Results of Cluster Synthesis....................................................... 21 Section 5 Results, Series That Are Present or Missing........ 22 II. A SIMPLE ORGANIC REACTION MEDIATES THE CRYSTALLIZATION OF THE INORGANIC NANOCLUSTER [Ga13(J.!3-0HMJ.!2-0H)18(H20)24](N03)15 29 III. NOVEL SYNTHEIS OF ALUMINUM 13 INORGANIC NANOCLUSTERS.................................................................................... 40 IV. NOVEL HETEROMETALLIC TRIDECAMERIC INORGANIC NANOCLUSTERS 57 V. ToF-SIMS CHARACTERIZATION OF M 13 INORGANIC NANOCLUSTERS 70 VI. SUMMARY OF INORGANIC TEMPLATED NANOCAGES 89 Pyridine-Imine Type Ligands............. 90 Pyridine-Pyrazole Type Ligands 95 Diketone Type Ligands.............................................................................. 98 Mixed Atom Binding Sites 99 Xl Chapter Page APPENDICES 101 A. SUPPLEMENTAL INFORMATION OF ANDERSON-EVANS CLUSTER REVIEW 101 B. SUPPLEMENTAL INFORMATION FOR GaB SYNTHESIS 113 C. SUPPLEMENTAL INFORMATION FOR AlB SYNTHESIS 124 D. SUPPLEMENTAL INFORMATION FOR HETEROMETALLIC NANOCLUSTERS.................................................................................... 161 E. SUPPLEMENTAL INFORMATION FOR ToF-SIMS ANALySIS............. 186 F. SUPPLEMENTAL INFORMATION FOR ORGANIC NANOCAGE SUMMARY 198 G. TEMPLATED ORGANIC NANOCAGES 203 BIBLIOGRAPHY 233 xii LIST OF FIGURES Figure Page 1.01. Survey ofInorganic Clusters. 2 1.02. Ball and stick and polyhedra view of Brucite lattice 3 1.03. Rotations of the Ml3 t Keggin cluster 4 1.04. Keggin M30 and other aggregates........................................................... 5 1.05. Hexagonal closed packed metal centers of a brucite lattice....... 6 1.06. Interconversion of Keggin clusters.......................................................... 7 1.07. Anderson Core as critical substructure for Ml3 clusters.. 9 1.08. Search criteria for various metal-oxo bindings from CSD 11 1.09. Substructures searched on the CSD......................................................... 12 1.10. Organic bind ligands commonly found in inorganic cluster crystal structures................................................................................................... 17 1.11. Ball and stick representations of common clusters 18 1.12. The distribution of the heterometallic series Gal3-xInx clusters................. 20 1.13. Additives that co-crystalize with metal clusters....................................... 22 1.14. Interesting clusters discovered in the search............................................ 24 1.15. Ball and stick representations of A. Mg, B. MIs and C. M32 Clusters ....... 25 1.16. Secondary CSD search criteria................................................................ 26 1.17. Mgring with disordered oxolate cation.................................................... 27 2.1. Screen capture of microscope image of the Gal3 crystals........................... 30 2.2. A. Crystal structure of Gal3; B Crystal structure of the pervious Al l3; C. HEIDI ligand; D. Crystal structure of HEIDI Stabilized Ga13..................... 31 2.3. Polyhedral (a) and ball and stick (b) representations of the crystal structure of the polycationic [Ga13(}t3-0HMp-OH)lsCH20)24]15+ 36 2.4 Crystal packing of the polycations [Gal3(1l3-0H)6(1l-0H)lg(H20)24]IS+ in 1............................................................................................................ 37 3.1. Known crystal structure the nitrosobenzene dimer. 42 3.2. Some of the commercially available nitroso group containing 42 3.3. The decomposition of the organic reductants post oxidation..................... 45 3.4. Other potential organic reductants screened 46 3.5. The isolated products from the pnictogen oxidation.................................. 48 3.6. Polyhedral representation of flat Ml3 Keggin-like nanoclusters................. 55 X111 Figure Page 4.1. Gallium and Indium Heterometallic nanocluster series, with distribution................................................................................................ 62 4.2. The heterometallic AlsIns cluster, synthesized by Z.L.M. 62 4.3. 1 is Ga13{Jt3-0HMJl2-0H)18(H20)2iN03)15 and 2 G~In6{Jt3-0H)6{Jt2- OH)18(H20)24(N03)15 64 4.4. Preliminary TFf Characterization trace.................................................... 68 5.01. Samples collected and screened 72 5.02. SEM of 1, showing only gallium present.................. 73 5.03. SEM of 2, showing gallium and indium present 74 5.04. Pascal's triangle distribution of isotope pattern 75 5.05. Isotope distributions of G~, 1114, and Ga2In2............................................ 76 5.06. Low mass range peak assignments.......................................................... 79 5.07. Mass spectrum of 1 from 550 to 1000 Daltons 81 5.08. Expansion of Spectra 1 at 495 Daltons 82 5.09. Stable M7 POM fragments :.............................. 83 5.10. Long range spectra oft with cluster assignments.................................... 84 5.11. Cluster that fit peak identification for spectra of 1................................... 85 6.1. Rigid amine functional spacers, both two-fold and three-fold symmetric.................................................................................................. 94 6.2. Crystal of Ligand 15g post deprotection................... 97 6.3. Dibromo spacers for coupling with Pyridine-Pyrazole 98 6.4. Saalfrank based ligands and diketo binding motif. . 99 B.l. X-ray Powder diffraction pattern of a fresh sample of 1........................... 114 B.2. X-ray Powder diffraction pattern calculated from single crystal structure of 1.......................................................................... 115 B.3. LC-MS trace of oily residue 115 B.4. TGA of Tridecameric Inorganic Nanocluster............................................ 116 B.S. Crystal Structure of GaB nanocluster 118 C.01. Crystal Structure of JTG51..................................................................... 124 C.02. Crystal Structure of Jasonl..................................................................... 129 C.03. Crystal Structure of JTG27..................................................................... 136 C.04. Crystal Structure ofJTG81..................................................................... 145 xiv Figure Page C.05. X-ray powder diffraction pattern calculated from the single crystal of JTG27........................................................................................................ 156 C.06. X-ray powder diffraction pattern of JTG27 157 C.07. X-ray powder diffraction pattern calculated from the single crystal of JTG81........................................................................................................ 157 C.OS. X-ray powder diffraction pattern of JTG81 158 C.09. TGA thermogram of JTG27 159 C.10. TGA thermogram of JTG81................................................................... 160 D.01. Ball and stick representations ofheterometallic crystal strucutres........... 161 D.02. Crystal structure of Ga7Il1(; 178 D.03. Predicted X-ray Powder spectra of Ga7In6.............................................. 185 D.04. TGA themogram of Ga7Il1(;...................... 185 E.01. Pictorial representation of one metal center 186 E.02. Pictorial representation of two metal centers........... 187 E.03. Pictorial representation of three metal centers......................................... 188 E.04. Pictorial representation of four metal centers.......................................... 189 E.05. Pictorial representation of five metal centers.......................................... 190 E.06. Pictorial representation of six metal centers............................................ 191 E.07. Pictorial representation of seven metal centers 192 E.OS. Pictorial representation of eight metal centers........................... 193 E.09. Pictorial representation of nine metal centers...... 194 E.10. Pictorial representation often metal centers............................................ 194 E.ll. Pictorial representation of eleven metal centers 195 E.12. Pictorial representation of twelve metal centers...................................... 196 E.13. Pictorial representation of thirteen metal centers 197 F.1. Crystal of ligand 15g post deprotection 198 F.2. Proton spectrum of compound 15g 199 F.3. Carbon spectrum of compound 15g 200 FA. DEPT spectrum of compound 15g............................................................ 200 F.5. COSY of compound 15g 201 F.6. HSQC of compound 15g 202 G.1. Template reactions................................................................................... 204 G.2. Computer models of ~L6 tetrahedron....... 209 xv Figure Page G.3. Acylation side products lla and 12a 210 GA. ORTEP of 5a single crystal structure........ 211 G.5. Proton NMR spectra of ligand 5a in DMSO............................................. 212 G.6. Proton NMR spectra of ligand 5a showing solvent and concentration effects are reversible.................................................................................. 213 G.7. Time points of5a in DMF with 2/3rds equivalents ofZn(BF4)2 215 G.8. Time points of5a in DMF with 2/3rds equivalents ofZn(OTfk.............. 216 xvi LIST OF SCHEMES Scheme Page 2.1. Organic reductants or ligands used to determine the functional group responsible for the formation of the GaB cluster. 32 2.2. Synthesis of Gal3 using CB[6] as an organic additive. 33 3.1. Reduction potentials of three nitroso containing organic compounds versus a SCE 43 3.2. Nitroso compounds that show activity and the isolated crystalline products yielded........................................................................................ 44 3.3. The oxidation with formation ofpnictogen oxides for the reactions 47 3.4. Oxime-Nitroso tautomerization................................................................. 49 3.5. Synthesis of "flat" AlB nanocluster using the organic reductants 51 4.1. Mixed group binary Metal combinations............... 58 4.2. Redox reaction forming Ga l3 and heterometallic clusters......................... 66 6.1. The general scheme to use an :MtL6 capsule as a template to form an organic nanocage, L' 89 6.2. Deprotection of benzyl ester ligand and metal-ligand self-assembly. 92 6.3. The capping first strategy.......................................................................... 93 6.4. The Ward based Pyridine-Pyrazole ligand self assembled and space filling surface with a BF4- counter ion encapsulated. 95 6.5. Modification of Ward Pyridine-Pyrazole ligand synthesis with distal functionality. 96 G.l. Yan's self-assembly tetrahedron.............................................................. 205 G.2. The general scheme to use an :MtL6 capsule as a template to form an organic nanocage, L' 206 G.3. Synthetic Scheme to make the L' Nanocages 207 G.4. Self-assembly of ligands 5 or 6 for templated nanocage....... 208 G.5. Projected route to get to intermediates 217 G.6. Alternate scheme for the capping of the ligands before self-assembly...... 219 G.7. Acylation, activation and capping condensation....................................... 220 xvii LIST OF TABLES Table Page 1.1. All hits from the M7(1l3-0)6 ring that are not in M130 search 13 1.2. All hits from the M13(1l3-0MIl2-0)18 ring 15 4.1. Ratios of the mixed group 13 cluster synthesis.......................................... 59 4.2. Starting material ratios compared to XRD and EPMA data of crystals 60 5.1. Summary ofXRD, EA and EPMA data 74 5.2. Low nuclearity species Peak Assignments 78 5.3. High Nuclearity species Peak assignments .. 85 A.1. All hits from the M6(1l2-0)6 ring 101 A.2. All hits from M6(1l2-0)12 ring................................................................... 109 A.3. All hits from M7(1l3-0)6 ring.. 110 A.4. All hits from M7(1l3-0MIl2-0)6 ring........... 111 A.5. All hits from M13(1l3-0MllrO)18 ring 112 B.1. Experimental Crystal Data from Ga13 119 B.2. Fractional Atomic Coordinates................................................................. 119 B.3. Anistotropic Displacement parameters 120 B.4. Selected Geometric Parameters 120 C.01. Crystal data and structural refmement for JTG51 124 C.02. Atomic Coordinates for JTG51 126 C.03. Bond lengths and angles for JTG5l.. '" 126 C.04. Anistotropic Displacement parameters for JTG5l 127 C.05. Hydrogen Coordinates for JTG51 127 C.06. Hydrogen Bonds for JTG51................................................................... 128 C.07. Crystal data and structural refmement for Jason1 129 C.OS. Fractional Atomic Coordinates for Jason1.............................................. 130 C.09. Bond lengths and angles for Jasonl........................................................ 131 C.lO. Anistotropic Displacement parameters for Jason1 133 C.lt. Hydrogen Coordinates for Jason1 135 C.12. Crystal data and structural refmement for JTG27 137 C.13. Bond lengths and Angles for JTG27 138 C.l4. Hydrogen Bonds for JTG27 143 xviii Table Page C.15. Crystal data and structural refmement for JTG8l 146 C.16. Atomic Coordinates for JTG8l 147 C.17. Bond lengths and Angles for JTG81....................................................... 149 C.18. Anistotropic Displacement parameters for JTG8l 154 D.01. Crystal data and structural refmement for JTGR36 (GaI01n3).................. 167 D.02. Atomic Coordinates for JTGR36............................................................ 168 D.03. Bond lengths and Angles for JTGR36 169 D.04. Anistotropic Displacement parameters for JTGR36................................ 171 D.05. Hydrogen Coordinates for JTGR36..... 172 D.06. Hydrogen Bonds for JTGR36................................................................. 172 D.07. Crystal data and structural refinement for dav4 (Ga71I16)......................... 179 D.08. Atomic Coordinates for dav4 (Ga7In6).................................................... 180 D.09. Bond lengths and angles for dav4 (Ga71I16)............................................. 180 D.10. Anistotropic Displacement parameters for dav4 (Ga71I16) 182 D.11. Hydrogen Coordinates for dav4 (Ga71I16)................................................ 183 D.12. Hydrogen Bonds for dav4 (Ga7In6) 184 E.01. Statistical distribution of one metal center............ 186 E.02. Statistical distribution of two metal centers............................................ 187 E.03. Statistical distribution of three metal centers.......................................... 188 E.04. Statistical distribution of four metal centers............. 189 E.05. Statistical distribution of five metal centers.. 190 E.06. Statistical distribution of six metal centers.............................................. 191 E.07. Statistical distribution of seven metal centers 192 E.08. Statistical distribution of eight metal centers 193 E.09. Statistical distribution of nine metal centers............................................ 194 E.10. Statistical distribution of ten metal centers 195 E.11. Statistical distribution of eleven metal centers 195 E.12. Statistical distribution of twelve metal centers.... 196 E.13. Statistical distribution of thriteen metal centers 197 G.1. Acylation results...................................................................................... 225 G.2. Condensation of 5a.................................................................................. 228 xix LIST OF GRAPHS Graph 4.1. Plot of gallirun numbers in crystal product versus starting material........... Page 61 I CHAPTER I ANDERSON AND ANDERSON-CORED TRIDECAMERIC INORGANIC NANOCLUSTERS Section 1 Background Polyoxometalate, hydroxyl/aqua bridged clusters and their variations have been known for quite some time. I, 2 There are a wide range of reported polyoxometalate clusters as well as many reviews covering them.3•16 The spectrum of clusters ranges from the Anderson-Evans cluster, which consists of small repeating units of the brucite lattice, 22to much larger 100+ metal discrete clusters. 17• This review will focus on the small metal clusters that are based upon the Anderson-Evans, Wells-Dawson, Keggin and tridecameric clusters. Background on Wells-Dawson clusters, Keggin clusters and their dimers will be presented. A focus on Anderson-Evans clusters will follow. Emphasis will be placed on how each of these clusters relates to the tridecameric cluster, with special attention given to the Anderson-Evans core. The polyhedron cartoons of these clusters are shown (Figure 1.01), where the vertices are bridging atoms and the metal center is in the middle of the each solid polyhedron. 2 A B C D Wells-Dawson Anderson-E"ans a Keggin (M 13t) II Flat"-M 13 (M13°) Figure 1.01. Survey ofInorganic Clusters. A. Wells-Dawson (M I8M'2), B. Anderson­ Evans (M7), c. Keggin (M13\ and D. Flat M 13°. The Wells-Dawson cluster (Figure LOlA) is an M I8 cluster that consists of eighteen octahedral metals encapsulating two tetrahedral atoms, that may not always be transition metals. Twelve metal centers form a "belt" made up of two rings of six that stack over each other to form a mirror plane along the equator of the molecule with an empty central space much like the ring of six from Anderson-Evans cluster (Figure 1.01B). Half of the belt is made up of a M6(1!2-0)6 ring that is isostructural to the first ring of the Anderson-Evans structure (Figure 1.01B). In addition, the cluster contains three metal centers at each end that comprise a trirneric cap. This trimer is very similar to one of the faces of a Keggin cluster. Anderson-Evans clusters contain an inorganic M7 core that has a hexagonal close packing anangement. The core position can be substituted with a variety of transition metals or non-transition metals such as the main group, alkaline earth, lanthanide or actinide metals.s Both the first reported Anderson cluster as a M07024 cluster, with its most-studied derivative bearing central iodine substitution (IM06024), have been studied extensively.2,23 Anderson-Evans clusters make up a large percentage of known inorganic 3 clusters while the tridecameric congers are rare in relation and can be considered as a subset of the Anderson-Evans cluster family. Figure 1.02. Ball and stick and polyhedron view of Brucite lattice of the same array.24 The brucite lattice could be described as a series of hexagonal close packed metal clusters that form a planar lattice of edge-sharing octahedra with the six perpheral metal centers of the cluster. That is, it is a series of interlocking Anderson core clusters that are offset when a peripheral metal center becomes the central metal of an adjacent cluster of seven metal ions. A Mnl9 cluster reported by Pohl et a1. contains a similar connectivity (Figure 1.09D) compared to a Fel9 cluster reported by Heath and coworkers which is more "layered" (Figure 1.09C).25.26 Counter-anions act as bridges between the planes of the brucite lattice. 27,28 Keggin clusters contain four trimers of octahedral metal centers arranged around a central tetrahedral metal center core. I. 29 The tetrahedral metal center of the Keggin clusters can be a variety ofmetals as wel1.3•4, 30 There are five different isomers ofthe Keggin cluster, a through E (Figure 1.03). The difference between the Keggin isomers is 4 in their successive rotations, 60° for each trimer surrounding the central metal (a31 , ~32, l3, 034, £35).3,36 The rotations changes the orientation of the timers from vertex-sharing to edge-sharing octahedra. There are different notations for different tridecameric clusters to differentiate the central metal coordination. The notation for a Keggin cluster is M13 t, while Anderson-Evans-like expanded tridecameric flat clusters are denoted M13°, where 0 and t refer to the coordination geometry of the central metal, octahedral or tetrahedral. Keggin clusters are also seen as units of larger clusters (Figure 1.04).3 Two M13 t Keggin clusters appear to dimerize with an ~ bridge of octahedral metals between the two units to yield a M30 cluster.3 Similar "trimers" are also formed where the clusters share a face of three octahedral metals.36,37 a y () E Figure 1.03. Rotations of the M13 t Keggin cluster 3 to produce the a to £ isomers. 5 a.-AlB / \ All·~ moieties \ \. '1 Figure 1.04 Keggin M30 and other "aggregates,,3, 36 There is also a class of clusters that falls between the Keggin and Anderson-Evans type clusters, the M13° clusters. Anderson-Evans structures are only a two-dimensional array of metal sheets that are bridged in the same manner as the small repeating unit of the brucite lattice. This larger class shares the same core of seven octahedral metal centers arranged in a hexagonal close packed array. The M13° cluster contains an Anderson-Evans-type planar Ml(ft3-0H)6M6(ftz-OH)6 core fragment that forms a central plane.38 Six M(HzO)4 groups are connected to this core via two alkoxo (ftz-OH) bridges; 39-41 hI d T e Anderson-type core ofthe groups a ternate above an below the central plane. the flat M13° clusters contains octahedral metals arranged in planar sheets, similar to the arrangement of seven concentric metal centers in a brucite lattice. 6 c D F Figure 1.05. Hexagonal close packed metal centers of a brucite lattice These new types of clusters have been called "flat" -Ml3, clusters, to distinguish them from the more spherical M l3 t Keggin clusters. The term "flat" is somewhat misleading, because these clusters are not flat like the Anderson-Evans core and brucite lattices; instead, they have outer metal centers that lie above and below the central planar core of seven metals. However, these flat clusters are not Keggin or "Keggin-like", as they lack a central tetrahedral metal ion. Furthermore, Keggin clusters are more spherical than planar, with a diameter of s.sA. The flat M 13° clusters themselves are more disc-like with a diameter of 12A and a cylindrical height of about 8A. As the Anderson-Evans cluster continues to grow', new metal centers are not added in the plane, producing more concentric rings or growing in the a or b directions.43 While the M l3 ° cluster has more metals that are not in the same plane as the core, they grow off in the c direction. A hexagonal close packed array is seen from above as just an Anderson-Evans cluster (Figure 1.05A). When more metals are added in the plane to expand into a brucite • The term "grow" may be a misnomer as it implies that there is a known mechanism for cluster formation, a discrete growth pattern. The term is only used here to describe the addition of new metal centers to an existing cluster or stable fragments. There have been a few predictions on how clusters grow.42. Goodwin, 1. c.; Teat, S. 1.; Heath, S. L., How do clusters grow? The Synthesis and Structure of Polynuclear Hydroxide Gallium(III) Clusters. Angew. Chern. Int. Ed. 2004,43,4037-4041. Work is continuing to determine stable fragments under mass spectrometry conditions in order to extrapolate back to nucleation sites, (Chapter V). 7 lattice, an original metal is now the center of the new adjacent unit (Figure 1.05B). Instead if the three new metals are added above the plane of the original seven, they can either be packed tightly in the center or offset to the outside. The same cluster is shown from both the top and the side to show stacking (Figure 1.05e & E). ----~ ----~ a Keggin (M13t) I(H)41(Si04)(W IZO IS)(OHh6 WelJs~Dawson IR4N 14(Si04}z(MoIS06Z) E Keggin (M I3t) AI 130 4(OHh4(OHZ) IS Anderson-Evans (NH4)6(M070 24) Figure 1.06. Interconversion of Keggin clusters to yield Wells-Dawson and Anderson clsters. When the Anderson-Evans core begins to grow· in the c direction, the clusters stop at 13, 15 or 19 metal centers. Smaller all-octahedral metal clusters that look like the Anderson core precursor have been synthesized.44 The vast majority of these clusters 8 contain Group 13 metals. The Anderson core that is contained in the M13°, M15° and M19° clusters are homometallic while the Anderson-Evans cluster often contains substitutions at the central metal. There have been several reported single substitutions of the central position.5,24 New additions to the variation of the central metal and an improved synthesis of these cores (personal communication) have recently been discovered. Metals of smaller radii are seen quite often in these hexagonal close packed arrays using oxo bridges while larger radii metals are almost exclusively seen in a bridging fashion between complexes where they are not as sterically confined.27, 45, 46 The larger radii metals are also seen using acetate bridges. The difference in ionic radii may play an important factor in cluster stability, which depends on both the charge of the metal and the high! low spin of electron configuration.47,48 It must be noted that data from the ionic radii on group 13 metals and their bond distances in metal clusters is missing in the Orpen paper.47 ------- 9 ..~----- Anderson-Evans (NH4)6(Mo70 24) Anderson-Evans (FeMo60 24)(OHh Figure 1.07. Anderson Core as a critical substructure for M13 clusters. The Lorenzo-Luis review of Anderson-Evans clusters is slightly dated and needs some updating. It does not mention larger inorganic clusters, while Casey's review describes briefly the flat M 13°cluster.3,s These reviews do not describe how some clusters are fragments of larger clusters; for example, the Anderson-Evans cluster is a fragment of the "flat" M13° cluster. The following sections describe how the Anderson- Evans cluster is a component of the larger M 13 °metal clusters and show relevant structural data. Section 2 Searches and Criteria There are two main databases to search for inorganic compounds, the Cambridge Structure Database (CSD) and the Inorganic Chemical Database (ICD).49 The structures found in the ICD are purely inorganic, while entries into the CSD database must have at 10 least one carbon atom per unit cell. Therefore, it is ironic that something as small as a disordered methanol in an inorganic cluster would allow for submission into the organic CSD. The CSD allows for the drawing of desired components and substructures, while the ICD is text driven with a choice of elements, but not their arrangement in space nor connectivity to each other. The results from the two databases are not easily compared because the search criteria are so different. Hits from data are not always accurate for searches being conducted. However, there is a way to combine multiple searches using Boolean operators to allow for better searching of the ICD. Searches were done with the CSD using stick compounds where "4M" represents any metal and 0 is any oxygen-containing bridging group (Figure 1.08). This ambiguity of the oxygen allows for the bridging ligand to be oxide, hydroxide or an oxo from an alkoxy group (0 can be OH, OH2, or OR). The same goes for the acetate bridge where it can be any R group from formic acid on up. The search does not state that the bridging motifs are not connected to each other; this allows for multidentate ligands to be included in the results. The search can also be restricted to transition metals. The 4M was purposely used in order to allow for the greatest potential ofmetal variety, including the alkali earth metals. Some clusters require organic stabilizing ligands as an external shell. Some are inorganic clusters, which only need organic additives to from (in some cases) in the solid state. The CSD searches yield only limited connectivity allowing for large variation in the types of structures found. The inclusion of OR and RCOO in the search 11 criteria yielded too many results, therefore constraints were added for geometry and rigidity of larger polymetallic clusters. • M4••• ,.M4•• M0 ........ : --"0 ¥4 .4. . ,, , , 0'" "0 M , , . . . o~'" "'9 ,4., ,, , I , . ••0. : ..0....: , , , , . .... .. .. I , , , ..M4 4M , , .M4" '4M t~W' ::4M , . •••• .4M ·····0···· ····0····· ~ 0" M4--------4M 6896 hits 4942 Hits 110134226 Hits3250 Hits ·· ... ....o.~ ,. ...... ........ .. .. .... o~.. ..r' M4' '" : M4 ~r·· o I ',, r. o , d : a'.... :0 •••• ......0..... ..0 . . • /' ........4M· 4M • '4M 4M"M{~') , , . , I • I , '0 , , . , , , I , 3835 Hits O~•..,;;-0 o~o ~ 1043 Hits735 Hits Figure 1.08. Search criteria for various metal-oxo bindings from the CSD. Multiple searches were performed with the CSD that had varying degrees of rigidity. Each search contained a fragment ofthe tridecameric cluster; each successive search increased the rigidity. The first was the M6 fragment, while subsequent searches were contained as subsets of previous searches. It was extremely difficult to perform the same search in the lCD. Specific elements and their stoichiometry could be chosen but no connectivity or structural data could be selected. When searching for any metal, the number of metals in a cluster could not be chosen. The lCD proved to be useful only if the exact composition or unit cell parameters are known. Specific clusters could be found, but a general search for a topology was difficult. The user interface is more text driven in nature than GUl as in the CSD. Screening hits was also more difficult because the data was tabular; to visualize the structure, a second program had to be launched for 12 each view. Previous queries made in the ICD could not be modified for future searches by utilizing the back function. A new query needed to be built each time, which increases the possibility of user input error from search to search. What took thirteen searches with the ICD could be done in one search with the CSD, where M = Mo, Ni, Mn, Ga, AI, In, Fe, W, Te, Cu, Co, Cr, which would allow it to fall under the CSD designation 4M. The ICD does allow for metal counts to be include but only with individual metals not with a wild card for all metals, therefore mixed metal clusters were not found. There were far too many hits with the first three searches, but with increased structural rigidity the specificity improved (Figure 1.09). Major omissions in the data were possible when looking for specific compositions. M7 V.rO)6 Anderson Fragment 3 M7 V.rO)6 V.2·0 )6 Anderson Core 4 Figure 1.09. Substructures searched on the CSD. For this review a ligand is bound to at least one metal of the cluster while an additive is co-crystallized out with the metallic cluster. The ligands found in the CSD search are shown in Figure 1.10. A summary of the hits from search 3 that are not in Search 5 of the M13 clusters are shown in Table 1.1. 13 Table 1.1. All hits from the M7(113-0)6 ring that are not in M l3° search Central CCDCRef. Metal AGICUO Zn AGIDEZ Ni AQOKAS Fe AQOKASOI Fe BEDBES Mn BEHJUU V BETFlQ Cr CASXEA Cr CUDGEN Co CUMSEI Na CUMSEIOI Na DAHYUH Mn DAQNUE CU DAWBAE Cr DAWBOS CI EMUJOL Al ESAXUR Li ESUWOE Cr HAVSAZ As HEFXUL Cr HEGBUQ Cr HOQHEA Mn HUHNED Ni HUHNIH Ni IBAXUF Cr INIMOH Cr IPUKEJ Mn IPUKEJOI Mn IPULUA Mn JAPQOH Cr JAPQUN Cr JAPRAU Cr JAPREY Cr. JINKAS Ca JOZCAC Cd KUPDII V LAHWIB Na LAHWOH Li MAYNEG AI MAYNIK Cr NECDUU Li NEWRAI Na NEWROW Li NITBEX Mn NOCJEU Na NOCKUL Cr NOCLAS Cr NOCLEW Cr First ring Mo Mo V V Mo V Mo Mo Mo V V Mo Mo Cu Cu Mo Fe Mo Mo Mo Mo Mn Ni Ni Mo Mo Mn Mn Mn Mo Mo Mo Mo Ca Cd V V V Mo Mo Fe Fe Fe Mn Mn Mo Mo Mo Second RlnglBridges As As Nd La Cu La V Ni Ni Mn Mn Ce La Pr Nd Ca Cd As Cu Cu Na Ligand L' LIO L" L" U 2 none none none None L" L" none None TFA TFA none L13 &MeOH none none none none L" L" L" none L16 L16 L17 L18 L18 L18 L18 U L' aniline L" Ul none none U3 Ul L" L16 Ll3 none none none Additive piperazine BEDT-TTF ferrocene ferrocene Hasenknopf'" HasenknopPo Khan" Khan" Favette" Kurata54 An" An" He" Chen" Chen" Zhange'O He" Cui62 Cui62 Shivaiah63 Affronte64 An" Li" Wery" Wery" Janas67 Ochsenbein 68 Ochsenbein 68 Kaziev" Ouahab70 Jones71 Jones71 Harden"' An73 An73 An73 An73 Goel"' Boulmaaz75 Kahn7' Shivaiah77 Shivaiah77 Shivaiah77 Shivaiah77 Abbati7' Saalfrank7. Saalfrank79 Bolcar'° Abbati'l Golhen'2 Golhen'2 Golhen'2 Reference 14 OCEZUS Mn In L19 Saalfrank83 OCIBAE Mn In L19 Saalfrank" OCIBEI Fe Mn L19 Saalfrank" OJEHEQ Mn Mo L'o Marcoux" OJEHIU Fe Mo L20 Marcoux" OJEHUG Mn Mo L12 Marcoux" PADPOA CI Cu Sm AcOH Zhang" PAKPAT Mn Mn L19 Saalfrank" PAKPEX Mn Mn L" Saalfrank'· PAKPIB Mn Mn L" Saalfrank'· PAZVER Mn Mn L13 Abbati" PAZVOB Mn Mn L13 Abbati" POZRAX Mn Mn Mn L" Brechin" QAYNEJ V V V none TBAOH Hayashi89 QUDBEW Na Ga L13 Abbati90 RAPDES Cr Mo none An" RAPDIW Cr Mo La none An" RAQGOG Mn Mn L19 Koizumi92 RASMEE Mn Mo UO BEDT-TTF Liu·' RASMII Mn Mo L IO BEDT-TTF Liu·' RASMOO Mn Mo L'o BEDT-TTF Liu93 TUMSUP Na Fe U' Caneschi·4 TUNYIK Mn Mn Mn benzoic acid Sun· ' TUQJAQ Zn Zn L17 Tesmer" TUSFOC Fe FE L" Oshio·' UDAZUU Al Al Al L24 Schmitt·' UDEBAG Al Al Al L24 Schmitt·' UDEBEK Al Al Al L24 Schmitt·' VEFQON Na Bi L' Mehring·· WADKOC Co Mo none guanidine LeelOO WATGUU Cr Mo Na U' An 'O! XALKOL V Mo none Duan'o, XALXOY Fe Fe L" Labat lO ' XEZFIR Ni Ni Ni L" Murrie104 XUTSIO Mn V L" Khan!Ol XUTSroOI Mn V L" Khan!Ol XUYRAK Pt W none guanidine Lee!" YAMHAW Cr Mo Ce none 18 An '01 YAMHEA Cr Mo La none 18 AnlO' 15 Table 1.2. All hits from the M13(Jl3-0MJl2-0)18 ring Data table from Search 5, The M13 Fragment CCDC Ref. Metal Ligand Reference BETCOT Mn L1 Murugesu108 JIDNIT Zn MeOH MorosinlO9 JONWUE Fe L2 HeathllO MEQZOX OFURAI Ta Mn L 3 L 4 Morgensem1II BrockmanII2 PAFKAJ Ga L 2 GOOdwin42 QAVDAT Mn L 5 Zaleskill3 SUZPUY Al L 2 Heath39 TAWWUK Zr MeOH DayII4 TAWWUKOI Zr MeOH DayII4 TAWWUK02 Zr MeOH DayII4 UCOTUB Mn L 6 Pohf6 UKUMlW Mn L 5 Denrinou-Samaral15 VEFPIG Bi L7 Mehring99 VEFQIH WESTOD Bi Fe L 7 L 2 Mehring99 GOOdwin25 WESWUM Fe L2 Goodwin25 WETCON Fe L 2 GOOdwin25 WETFOQ Fe L 8 GOOdwin25 The eSD data set was current as ofNovember 2006, and validity of the data can only be conftrmed through that edition. Additional data has been provided via personal communication and research done by the author and co-workers that is included in this dissertation. A question remains as to how useful the eSD and leD can be due to the number of false positives and false negatives found, since the data found is only accurate to the parameters entered but not always accurate for what is actually needed. Each structure that is out put from the search as a hit should be evaluated carefully to conftrm its accuracy to the criteria. Section 3 Ligands and Stability The searches outlined in section 2 yield a large variety of clusters which contain organic supporting ligands or that co-crystallize with organic additives. Smaller monodentate ligands like pyridine seem only form monometal complexes. The Gal30 16 cluster had previously been synthesized using stabilizing aminocarboxlate ligands, such as HEIDI.42 The only example of an unstabilized AIl3 0 cluster was produced in low yields requiring both caustic conditions and long reaction times.40 A very similar MIs cluster was synthesized using HDTP as s stabilizing ligand.98 There were also a variety ofmultidentate ligands like HEIDI and HDTP used to stabilize metal cluster.25, 39, 42, 50, 98, 110 This led the way for researchers to explore even larger ligands like EDTA or DTPA. 17 OH HO ~IH0:¢r0H "­ N ~O~50H n OH OH HOVOH HO OH HO I HO,/"'-/ N ..& OH 0 L2 0 L4 L5 HEIDI HO HOO~50H HO H0=r H~OHOH \..../""OHHO HOt ) HO/'-...../O, HO,/"'-/HO HO L9L6 L7 L8 0 0 0 1 0 0 N~NyO 7} 6 NH:~~ 0 ~ I OH HO 0 OH ..& ..&HO ~ cr 0 0 2 0 3 0 4 0 5 0 6 0 HO HO aOH HO\y(JOH f' ~ H2~OH \..../""OH N- HO,/"'-/ HO / 0 7 0 8 0 9 L20 L21 OH /O~N~OH V L24 L25 HPDTA OH O~ 0yOH iN~N) HO 0 (0 iN~OH EDTA DPTA HO 0 Figure 1.10. Organic binding ligands commonly found in inorganic cluster crystal structures. 18 The coordination chemistry of gallium is of interest because of its similar ionic radii to iron.48 Gallium also poses an interesting target because of its use in PET scanning. I 16, 117 The majority of the ligands for Ga are catechol I 18-120 or aminocarboxolate derivatives. 39 Recently, an unstabilized Gal3 cluster was synthesized.41 Since then, a faster and cleaner synthesis of both the Gal3 cluster and other M 13 clusters has been reported in Chapters II-V. 121 A 8 c D Figure 1.11. Ball and stick representations of common clusters A. HEIDI bridged MI3°, B. unbridged M 13°, C. HEIDI-bridged M 19, D. unbridged MI9 The actual number of discrete tridecameric clusters is much smaller than the twenty hits from the CSD. In fact, there are only about eight that count as containing the M 13° core, a few are MIs or M I9 clusters. 25 ,98 These are distinct from the Pohl M I9 cluster (Figure l.11D), which is more Anderson-Evans like because of the pattem of growth from the central core.26 The Pohl M19 cluster is filling in between the existing outer shell metals with more centers to make a continuous array of planar metals.42 We have synthesized a series ofheterometallic M13° clusters. We now have the complete set of Ga13-xInx, where 0 2: x 2: 6. Two of the corresponding aluminum and indium series have been synthesized, AI l3 and A18In5. Analogous heterometallic clusters 19 were not observed in the results from either the CSD or the ICD. Despite the lack of substitution in the central ring, the second ring substitutions may help determine cluster growth and stability of precursor fragments in how the clusters form. 42 Elemental analysis will only tell the relative abundance of metals present. A problem with x-ray structural analysis of heterometallic clusters is their high symmetry (D3d), which often leads to disorder within the heterometallic cluster. However, the ratio of metals can be determined based on occupancy factors by counting the electrons of the metals in the symmetrically equivalent positions (Figure 1.12). Ga 13 Ga 12 1n Ga aln s Ga 71 nS Ga 11 1n 2 Ga 10 ln 3 G a 9 ln 4 Fi gu re 1 .1 2. T he d is tri bu tio n o f t he h et er om et al lic se rie s o f G a1 3-x 1n x cl us te rs . N o 21 Section 4 Results of Cluster Synthesis Anderson-Evans clusters are quite stable, which is why the original M07 Anderson cluster can easily be used as a starting material for substitution at the central position; many examples are known in which the core metal has been exchanged.s This review is quite old though, and there are more examples that have been discovered since its publication, in fact more than 70 new Anderson-Evans and cored clusters have been synthesized (Table 1.1 & 1.2). The M07cluster now seems quite easy to alter. The stability of the Anderson-Evans cluster, as well as larger structures built off of it, may offer some insight into how these clusters form. 42 New work has augmented the field of inorganic nanoclusters by the use of organic reagents and additives to form nanoclusters. The use of organic reagents, such as nitrosobenzene, can allow the synthesis ofmultiple metal (Chapter II).41 The same clusters and new analogs have been synthesized by using DBNA, however the organic by-product has not been isolated. 121 Other additives have also been used to induce crystallization and/or to help to nucleate the cluster. Fedin's work with Cucurbit[6]uril (CB[6]) is an excellent example of organic additives serving as nucleation sites (Figure 1.13).122,123 The same additive has not always yielded the analogous cluster with different metals. Fedin used CB[6] in an attempt to make the flat AI13 °cluster3 but instead obtained the Al13 t Keggin cluster.123 It is surprising that there are no reports using the analogous additives CB[7] or CB[8] to co-crystallize similar clusters. The use of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) as an additive has also been in the crystallization of these clusters (IBAXUP9, INIMOH70 , NOCLAS82, NOCLEW82" 22 additives may not be entirely innocuous, in that they in fact modulate the electronics of the inorganic cluster.124-126 OH' (]N N~N2C: Figure 1.13. Additives that co-crystalize with metal clusters Metals of different oxidation states can be contained in the same cluster. This is quite common for manganese.80, 81, 87,112,127 These clusters have a potential use as single molecule magnets. 18,26, 51, 62,108, lIS, 128-135 For these mixed oxidation state clusters it appears that the oxidation state of one of the reagents changes throughout the reaction from starting material to crystal. Hydroxyl oxygens are the most common heteroatoms used as bridges. The only heterometallic clusters observed in the literature ofAnderson- Evans cord clusters are the Anderson-Evans clusters themselves.5 The very large clusters seem to have different metals involved in different roles as bridges between smaller subunits. Section 5 - Results, Series that are present or Missing The data obtained from the CSD is significant, but there were many other structures of interest that were found that were not found in the CSD search. A search of the ICD found the original Ah Anderson-Evans cluster; however the analogous Ga7 and In7 clusters are not present in the database. We expected to see the Ga7 cluster, as that 23 fragment was observed in our heterometallic series. The large ionic radius of indium explains why we did not see the In7 Anderson-Evans cluster.48 A very interesting structure that appears in the M6 core but not in the M7Anderson-Evans or M7Anderson­ Evans fragment searches is an In6 ring that is the same as the core of the tridecameric clusters, Figure 1.14C, (BEQRARI36). Additionally, there is the same ring but with manganese or iron inserted into the central position (OCEZUS, OCIBAE, OCIBEI83). This is also true of both the Anderson core and the Anderson fragment search. From the M7 Anderson-Evans core CSD search we do find a M I5 isomer that is not included in the tridecameric search (UDAZUU98). Other clusters of interest were found which contain thirteen or more metals that have the same binding as the MI3° cluster, but the three metals that are above and below the M7 core are now offset from the outer rim but instead are packed directly above the core. There are a few examples of cluster that are still M\3° but spherical (Figure 1.14A), in this case the metals added are in the voids above the plane between the central and two adjacent ring metals (Figure l.05D & F). The Anderson-Evans core forms an equator; this plane contains the most metals per plane, additional parallel to the core. There can be three additional metals added to the top and bottom of the ring to make a sphere (CUDGEN57, DAQNUE6\ DAWBAE62, DAWBOS62, JIDNITI09, MEXZOXlll , PADPOA85, TUNYIK95). The second layer above the equatorial plane does not need to continue in the hexagonal close packed array. Similar to the M\30 clusters where additional metals are added outside the Anderson-Evans core the addition metals can be added in a column above the first ring only offset by 30°. Typically, this layer contains 24 six co-planar metals (KUPDII/6), though sometimes only four metals are present in the second layer with vacancies at 1800 (POZRAXIOS, YEBLIB137). Three more metals can be added to the second layer in distal positions with the third layer offset on top for a M25 cluster, which stacks in layers of3,6,7,6 and3 metal centers, Figure 1.14B. (BETCOT1os) There is one example where the growth is not symmetric: additional layers are only on top of the Anderson-Evans core (Figure 1.14B) (UKUMIWI15). A cB Figure 1.14. Interesting clusters discovered in the search. A. M13°Sphericical 3,6,3 metals, B. 3,6,7,6 and 3 array ofMn centers, C. In6 ring. Two Ms clusters were discovered through other searches of the literature. The clusters Ais 44 and Gas (PAFJUC42), though not Anderson-Evans or M13 clusters, have portions that are structurally similar in about half of the complex. The Ms cluster has six metals that closely resemble the M7 core of the indium Anderson-Evans cluster. If one of the six metals from the first ring of the core is removed, the two adjacent metals will twist out of the plane to relieve the torsional strain imposed by the planarity of the seven metals. These clusters may help to explain the stability of other clusters like the M13 as 25 well as fragments that are observed from ToF-SIMS experiments to be discussed later (Chapter V). A Figure 1.15. Ball and stick representations of A. M8, B. MIs and C. M32 Clusters The original search for tridecameric and Anderson-Evans clusters and component fragments only looked for a ring of six metals. The CSD does not allow definition of cyclic or repeating units. Follow-up searches copied the M6(~2-0)12 fragment for the larger Mn(~2-0)2n rule. The same 2N+2 rule for organic degrees of unsaturation applies to inorganic rings as well. A ring has one degree of unsaturation, which subtracts two bridges from the corresponding chain. These other ring structures may be of interest to help explain the stability of the clusters. There are clusters containing up to twelve metals, which would begin to resemble the second metal shell in a brucite lattice. These larger ring systems have a cavity size the same as the smaller Anderson-Evans clusters and could be used as templates or nucleation sites for the formation of these smaller clusters. The identical search was performed for n = 7,8,9, 10, 11 and 12. The search in the CSD that yielded hits was the n = 8 ring. 138, 139 A structure was found that has a single oxo bridge between ring one and ring two, opening up a position on each metal of 26 ring one and therefore changing the bonding geometry between the Anderson core and the second ring ofmetals.71 There might need to be an additional review of metallic ring structures that are not solid in the middle such as those given in (Figure 1.16A).131, 140,141 Figure 1.16. Secondary CSD searches criteria The modified M13 structure should yield structures that fall between the previous searches of the Anderson-Evans cluster and the rigid tridecameric cluster. It also presents the possibility of other heteroatoms acting as bridging or coordinating ligands. The single bridged M13 cluster yielded thirty nine hits. The previous tridecameric search hits are included in this data set. Some new observations include the incorporation of larger metal ions in the other ring, as well as much larger ligands that contain functionalized pyridine rings. There are fifteen analogous Ms ring clusters found in searching the CSD, Figure 1.17A. Eleven of them did not require a larger ligand to force the formation of the larger ring, however most encapsulate an ion such as oxolate (AWEWEEI42 , 27 SWJYOV & SEJYUB I49, TASMlKI5o, XOVPED151 ). The remaining four used the functionalized p-tert-butylsulfonylcalix[4]arene and large diameter lanthanides to form the cluster, Figure 1.17B and c. 152 o OH 0 IIII 8 -8 IIII oo 4 Figure 1.17 A Ms ring with a disordered oxolate cation, and calix[4]arene ligand supported clusters SUMMARY Recent searches of the CSD and lCD show there are numerous clusters that contain the Anderson cluster as a fragment in their full structure. Despite the wide variety of metal substitution seen at the central metal substitution of the Anderson-Evans and Keggin clusters, there are few other heterometal1ic structures found. Database updates are far behind the research, and the interfaces are not always friendly. It is crucial that databases provide an option to combine a completely inorganic search with a full CSD search. Prior to this, the M I3 0 clusters have typically been called tridecameric clusters, though an extensive review by Casey distinguishes them from a classical Keggin cluster by calling them "flat-MI3" clusters. We have contributed to this field with new substitution at the core position and with our expansion of the M13° chemistry as we11.41 • 28 121 The dilemma presented by this research is in the naming of the flat tridecameric clusters because of their different expansion on the Anderson-Evans core. These cluster are already showing their potential use as synthons. These clusters will need their own name and naming scheme as more of these clusters are synthesized and used. 29 CHAPTER II A SIMPLE ORGANIC REACTION MEDIATES THE CRYSTALLIZATION OF THE INORGANIC NANOCLUSTER [Ga13(J.!3-0H)6(J.!2-0H)18(H20)24](N03)15 I initially identified the novel cluster and performed the collection of the Single Crystal XRD data. I was the primary contributor to the optimization of the synthetic conditions including the determination of the active functional group and developed the purification procedure. Dr. Elisabeth Rather was helpful in solving the crystal structure. Dr. Victor Kravtsov was helpful in verifying the charge state of the cluster. Dr. Paul G. Nixon and Dr. Takuji Tsukamoto contributed to this publication by providing the original organic reagents. This work was published in Volume 125 of the Journal ofthe American Chemical Society in February of2005. Dr. Prof. Darren W. Johnson was the principle investigator for this work. 30 A series ofNMR titration experiments were run to determine the binding of Ga(III) with proprietary organic ligands developed by Chemica Technologies, Inc. The NMR reaction was allowed to evaporate and yielded large crystals (Figure 2.1). Evaporation of the solvent from the experiment solutions yielded crystallographic grade 2.2A). However, the crystal structure does not contain the organic ligand from the nanocluster has been previously reported (Figure 2B), I and Goodwin et al. had theorized organic ligand-stabilized clusters have also been isolated (Figure 2.2C and D).2, 3 .... ~ - Figure 2.1.Screen capture of microscope image of the Gal3 crystals 31 o~-->--O" ~ HO HEIDI A ne Figure 2.2. A. Crystal structure ofGal3; B Crystal structure of the pervious A113; c. HEIDI ligand; D. Clystal structure of HEIDI Stabilized Gal3. Since there were no organic binding ligands in the structures, and Ga(N03h recyrstallized on its own will not form [Gal3()l3-0HM)lz-OH)18(HzOb](N03)JS clusters like this, the organic additives must have had some effect. Follow-up experiments to determine the active functionality of the proprietary ligand yielded the discovery that the nitroso functionality is necessary for the formation of the Ga nanocluster. Nitrosobenzene acts as an organic reductant by reducing the nitrate counter ions; this forces the formation of the multiple metal [GaD()l3-0HM)lz-OH)18(HzO)Z4](N03)ls inorganic nanocluster. The other functionalities from the proprietary ligand yielded ligand substituted products or starting materials. A functional group testing approach was taken to determine the active functional group. Each functionality of the ligand was tried individually. Multiple combinations of functional groups were tested also for reactivity. 32 Proprietary 10 C'I Gn(NO ) • 6 H ° Cmpd. J J 2 CD,OD. cv"p. o 10"'-1 Ga(NOJ)J' (i H20 CHJOH. cvap. N Pyridine n 10 cq Ga(NOJh • (i H20 Ga(2,6-Lulidiueh(NO,hCH.,OH, evap. N 2.6-Lutidiuc Nilrosobcnzenc ~ ~(o- - 0 NiLfobenzene Scheme 2.1.0rganic reductants or ligands used to determine the functional group responsible for the formation of the Gal3 cluster. After the publication of our method utilizing the nitroso functionality as an organic reductant, another group published research yielding the same [Gal3(1l3-0HMIl2­ OH)18(H20)24](N03)15 inorganic nanocluster. However, their cluster co-crystallized with cucurbit[6]uril (CB[6]) and an oxo bridged Ga32 species.4 The Fedin group was not sure how their additive aided in the formation of the flat Ga l3 clusters. Their group continues to use CB[6] as an organic additive to make other clusters in the same manner, allowing our two routes to diverge.5,6 They were able to visually sort their crystals based on their physical morphology from just CB[6] and the Ga32 cluster. 33 Cucurbil[6]uril +H20, pyridine pH 1.8 Scheme 2.2. Synthesis of Gal3 using CB[6] as an organic additive.4 The following pages summarize our initial publication of the synthesis, isolation and characterization of the flat Gal3 nanocluster. Other work on these types of clusters is in the chapters which follow. Included is an in-depth characterization chapter and a discussion of future works. Developing predictive design strategies to prepare inorganic cluster compounds has attracted much research interest, due in part to the potential applications of these novel materials.2,7·) I We present a potentially new synthetic strategy for preparing discrete inorganic clusters, and we use this strategy to prepare the first crystalline example of an inorganic tridecameric Ga cluster. By using Ga(N03HH20)6 as a nitrate source for the conversion of nitrosobenzene to nitrobenzene - which is known to proceed using nitric acid - robust crystals of the nitrate-deficient gallium cluster first synergistic use of a simple organic reaction to mediate the fOlmation of a polynuclear inorganic cluster compound. Studies on polycationic metal oxo- and hydroxo- aggregates of gallium and aluminum have centered around understanding their environmental impact (e.g. soil 34 science, water treatment), 10,12-14 determining their biological relevance (e.g. toxicity and transport ofmetallic species),14, 15 and preparing new materials (e.g. catalysis, magnetism, porous solids). 16-18 In this context, aqueous complexes of gallium(III) have received less attention than their aluminum counterparts, largely due to difficulties in preparing stable single crystal forms of these clusters. 13 Solid state and solution investigations on the formation of inorganic gallium clusters reveal that the majority of the compounds are polyoxycations based upon the modified-Keggin structure, which possesses octahedral peripheral gallium cations bridged to a central tetrahedral Ga(III).17, 18 While the presence of chelating organic ligands stabilizes a range ofpolynuclear clusters and allows for their crystallization,2, 3, 7,19 the structural characterization of purely inorganic Ga(III) clusters analogous to the AlI3 clusters is lacking. l , 13 We report the single crystal structure of an inorganic Gal3 cluster l' prepared using a simple organic reaction to drive the formation of the crystalline inorganic cluster. Robust crystals up to 15 mm3 in volume of [Gal3(1l3-0HMll­ temperature ofa methanolic solution ofhydrated Ga(N03)3 in the presence of nitrosobenzene. In this process the nitrosobenzene acts as a scavenger of nitrate ions and facilitates the nucleation ofGal3 clusters via a redo process in which the nitrosobenzene is oxidized into nitrobenzene with concomitant reduction of some of the nitrate counter ions. High-Pressure Liquid Chromatography-Mass Spectrometry (HPLC-MS) and IH NMR spectroscopic data prove that nitrobenzene is indeed formed in the crystallization • Crystal data for 1: Trigonal, R-3. a =20.214(3), C =18.353(4) A, volume =6494.7(19) N, Z =3, D, = 2.127 g cm'" p= 4.128 mm", F(ODO) = 4116. 2e~ =52.80· (-24 =h =25, -25 =k =25. -22 = I =22), Final residuals (for 228 parameters) were RI =0.0310 for 2500 reflections with I> 2o(l), and Rl =0.0349, wR2 =0,0988, GooF =1.035 for all 2831 data. Residual electron density was 0.949 and 0.567 eA'. 35 process. t Furthermore, it is known that nitric acid can oxidize nitroso derivatives into the corresponding nitro compounds; this procedure simply represents a milder form of this reaction, in which nitrate oxidizes nitrosobenzene at a slightly acidic pH?O-22 In effect, as a result of consumption of some of the nitrate counter ions of Ga(N03)3, the remaining gallium-containing species must form a higher nuclearity cluster where the ratio of nitrate to gallium(III) is less than 3: 1. In this case, the stoichiometry descends to 15:13. In this redox process one GaB cluster must be produced per 24 nitrosobenzene oxidized. t 'H NMR and LC-MS spectra of the mother liquor remaining after crystallization of 1 showed peaks characteristics of both nitrosobenzene and nitrobenzene. 36 A B Figure 2.3 Polyhedral (a) and ball and stick (b) representations of the crystal structure of the polycationic [Ga13Vt3-0HM/l-OH)18(HZO)Z4] 15+. The crystal structure of the mixed hydroxo/aquo cluster 1 reveals the compound does not crystallize as the modified Keggin structure seen in the related AI 13 or MAl 12 c1usters,23,24 but rather is similar to Gal3 clusters stabilized by supporting ligands, where the central gallium is octahedral, not tetrahedral.1 Each tridecamer consists of a central Ga(lll) bridged via hydroxyl groups to six surrounding galliwn cations forming an inner core of seven edge-shared Ga(O)6 polyhedra. The six inner polyhedra are further vertex- shared to six peripheral tetrahydrated Ga(III) ions generating a disk-like compound with an effective diameter of ca. 1.81 urn and a thickness of ca. 1.03 nm. The central, inner lIn the structure of the related aluminium tJidecamer reported by Seichter el al.,J. Seicbter, W.; Mogel. H.-J.; Brand, P.; Salah, D., Crystal Structure and Formation of the Aluminum Hydroxide CloJide [AI13(OH)",(H,O)",lCI" • 13 H,O. Eur. J. Inorg. Chern. 1998,795-797." not all hydrogen atoms positions could be determined. Therefore, charge balance considerations based on the number of chloride counterions were used to determine the number of hydroxo versus aqua ligands, and it was assumed that only the hydroxo ligands were bJidging. The structure of 1, in which all hydrogens atoms from the coordinated O-H groups were located in the FouJier difference map, corroborates this. 37 Ga(IlI) lies at a special position on the "3 axis of the unit cell and is coplanar with respect to the six surrounding edge-shared Ga(O)6 polyhedra (mean plane deviation of 0.06 to 0.07 A). The distances between edge-shared gallium cations and the corresponding oxygen atoms d(Ga-)..t3-0H) are in a range of 1.96 to 2.15 A. The six external Ga(O)6 polyhedra are bonded to the inner core of seven Ga(IlI) each via two vertices with corresponding distances d(Ga-)..t2-0H) of 1.91 to 1.92 A. The peripheral Ga(IlI) are each coordinated to four water ligands with distances d(Ga-OH2) in a range of 1.98 to 2.01 A. Figure 2.4 Crystal packing of the polycations [Ga I3()..t3-0 HM)..t-OH) 18(H20b] 15+ in 1 representing the stacking of sheets in an ABCABC mode orthogonal to the z-axis (a) and orthogonal to the y-axis (b), hydrogen atoms, counter-anions N03- and water molecules have been omitted for clarity. The peripheral tetrahydrated gallium centers deviate from the mean plane of the inner core formed by the seven edge-sharing cations by ca. 30° and they are positioned alternatively above and below the plane of the Ga7 core. The main difference with respect to the structure of [AI dOHh4(H20)24]CI 15' 13H20 lies in the crystal packing adopted by 38 1 (Figure 2.1.2): the Gal3 clusters crystallize in a hexagonal array. The polycationic units arrange in layers parallel to [001] and repeat in an ABCABC mode along the z-axis with an interlayer separation of 6.12 A. Cluster 1 is a highly hydrophilic compound with a :. surface rising with hydrogen bond donors and acceptors. These particles are completely surrounded by counteranions forming shells around the polycations through an intricate hydrogen bonding network in which interstitial N03- and uncoordinated guest water molecules interact with coordinated water and hydroxide ligands with distances d(O'''O) in a range of 2.57 to 3.00 A. In summary, a straightforward method to generate mixed aquo/hydroxo gallium clusters in the form of large robust single crystals has been presented and provides an alternative to the hydrolysis of the cations in the presence of base, which usually results in the formation ofpoor quality crystals. Further work is currently underway to investigate the properties in solution of the Gal3 clusters. These purely inorganic aggregates might be relevant as starting materials for the generation of a wider range of particles via exchange of the water ligands with appropriate organic species. We are exploring the generality of our synthetic route to see if treatment of other metal nitrate salts with nitrosobenzene provides higher nuclearity metal clusters as well. Supporting Information Available: Crystallographic data for 1 in .CIF format is available as CSD 414322. These data can be obtained from the Fachinformationzentrum (FIZ) Karlsruhe, D-76344 Eggenstein-Leopoldshafen (Germany) www.fiz­ informationsdienste.de. This material, details of the synthetic procedure and x-ray 39 powder diffraction patterns are also available free of charge via the Internet at http://pubs. acs.org. 40 CHAPTER III NOVEL SYNTHESIS OF ALUMINUM 13 INORGANIC NANOCLUSTERS The synthetic procedure in this chapter was developed by a number of lab members including Jason T. Gatlin and Zachary L. Mensinger. Zachary L. Mensinger contributed substantially to this chapter by participating in the development of a standard synthetic procedure. I was the primary contributor to the optimization of the synthetic conditions and developed the purification procedure. Dr. Lev N. Zakharov was helpful in solving the crystal structure. Dr. David MacInnes was helpful in reviewing and editing the manuscript. This work has not yet been published but will be submitted in the summer of 2007 to the journal Inorganic Chemistry. Zachary L. Mensinger initially identified the alternate nitroso reductant for cluster synthesis, which yields the identical cluster to the Nitrosobenzene synthesis. Dr. Prof. Darren W. Johnson was the principle investigator for this work. 41 Since the synthesis of our frrst "flat"-Ga130 cluster l , we sought to explore the generality of the reaction. There were two different directions of experiments to explore; the organic side and the inorganic side. The first was to determine if the identical unstabilized Ga13° cluster can be made with other reductants and determine the importance of the nitroso functionality. The second was to determine if other similar clusters could be synthesized via the same reaction conditions. Chapter 2 will discuss the results of the organic experiments, and Chapter 3 will address the synthesis of other Ml3 ° nanoclusters via the same reaction. We began changing the conditions of the crystallization in hopes of increasing the isolated yield of the nanocluster. We were hoping to see what drove the crystallization of the nanocluster and to determine if it was the observed oxidation of nitrosobenzene and, therefore removal of the nitrate counter ions or if it was the evaporation of the solvent. Crystallizations set up in the refrigerator or freezer yielded large, stable, colorless crystals very quickly. However the only crystalline product isolated was the dimer of nitrosobenzene which can be isolated by lowering the temperature or by chromatography of the reaction mixture before completion. This structure was already know and was present in the CSD (reference code: CAZBZOlO and JTG46.?·3 42 Figure 3.1. Known crystal structure the nitrosobenzene dimer. (Orthorhombic P, Pbcn, a = IO.292(l)A, b = 13.796(1) A, c = 15.005(1) A, a = f3 = y = 90 °V = 2137.8 A3, Z = 8) Since determining that the nitroso functionality was the active functional group, commercial suppliers were searched for other nitroso-containing organic compounds as well as potential reductants with similar electrochemical potentials Figure 3.2. Typically, it is difficult to determine reduction potentials for organic compounds and only a few have been determined (Scheme 3.1).4 ON·N.o·NHNO NO ON \ HOm /""'N JlNN02(y :::,... I ~ NONHH 6' 6 o-nitrosotoluene I-nitroso-2-hydroxylnaphthlene guanidine Cupferron I-nitrosopYffolidine ON.N'''· I ¢ NOO=S=O 0. N=NNO ¢ Y­ I ~N~ /N...... --t- 0 diazald N-nitroso-dibutlyamine 4-nitroso-N,N-dimethylaniline tert-nitrosobutane dimer Figure 3.2.Some of the commercially available nitroso group containing compounds 43 0.:­ 6 Nilrosobenzene 0'-"0 N +.35 V_ 0.:- V &+HzO -.35 V o-Nitrosotoluene ,N, ,O'NH :9 0' I 4 -'N 0+.84 V 0' 'N' 'NH46 +HzO + 2e- + 2H+ (aq) --.84 V ­ 6:.:,..1 Cupferron Scheme 3.1. Reduction potentials of three nitroso containing organic compounds versus a SCE.4 All the reactions were set up following the same procedure as the synthesis with nitrosobenzene, except for the exchange of organic reductants in the same stoichiometry. Scheme 3.2 shows the crystalline products isolated from the reactions of the alternate reductants with Ga(N03)3' Cuperferron has been known to bind copper and iron in a similar manner, hence the name, as well as aluminum.5 The nitroso functionality of the guanidine and the diazald are not stable: both compounds denitrosolate under reaction conditions, with or without metal being present. From the series of organic compounds in Figure 3.2, only one, N,N-Dibutyl-N-nitrosoarnine (DBNA), yielded the same flat Ga130 nanocluster. Figure 3.3 shows a side-by-side comparison of the two reactions with the different nitroso compounds: nitrosobenzene (on the left) and DBNA (on the right), both of which yield the nanocluster in respectable yields. 44 Ga(Cup)3 ON'N/ I MeOH Slow EVl\~.O¢O wi or wlo Ga(N03)3 Gn(N03lJ + ~O .. "Gau" ~N~ MeOH Slow Evap. Scheme 3.2. Nitroso compounds that show activity and the isolated crystalline products yielded. The difference in the two reactions is very clear. The yields are higher in the DBNA reaction, most likely because of the great ease in which we can isolate crystals by just decanting the oil byproduct. The new organic additive DBNA can also be recycled and reused for fUlther reactions making this synthesis greener than using the nitrosobenzene. This suggests that the organic byproduct of the cluster synthesis with DBNA is not as stable as the nitrobenzene product of the nitrosobenzene reductant. Current works to track down the oxidized product of the DBNA reductant have not been successful. We hope to determine if the reaction can be used in the future as gentle organic oxidant. 45 , Figure 3.3. The decomposition of the organic reductants post oxidation. Nitrosobenzene product and DBNA product (left to right) Tweaking the conditions for Gal30 cluster formation allowed us to synthesize the analogous AI 13 ° cluster. This new organic reductant allows for the formation of our previous Ga13 °cluster in a higher yield and allowed for the isolation of the previously known Al 130 nanocluster as well with the same reaction conditions. The Fedin group also tried to use their CB[6] strategy to synthesize the flat AI 13 ° nanocluster, which they reported to Casey6 as a personal communication, but their later published results indicate lthat they in fact synthesized the Keggin Al 13 cluster not the "flat"-AI13 ° cluster.7 Due to the other stability issues the use of nitrosobenzene will be discontinued in favor of DBNA. 46 We tested a variety of other organic compounds that we believed were easily oxidized and that do not contain the nitroso functionality as possible reductants for the formation of the flat Ga13 0 nanocluster Figure 3.4. As of yet none of them have yielded a metal cluster. phenylsulfide phenyl Sulfoxide o~v II ~N'o ~S~U ~N' \ obenzyl Sulfide n-propyl Sulfoxide Benzofuroxan ,":: ~Oec? ~ OR Decylaldehyde 2-Isonitrosoacetphenone Malachite Green I(Phenylglyoxaldehyde Oxime) Figure 3.4. Other potential organic reductants screened One conversion of interest with low oxidation potential is the oxidation of a phosphine or an arsine to its oxide. 4 The ease of oxidation of the pnictogens follows the established trend (P>Sb>As), with P the easiest to oxidize. It is clear that phosphines are easily oxidized to phosphine oxides while arsines are more stable to oxidation. Triphenyl Bensoin-a-Oxime ~O o OR N....... Triphenyl Phosphine Salicylic Aldehyde 47 phosphine, triphenyl arsine and their oxides are used extensively for initiating polymerization reactions and as ligands in transition metal complexes and catalysis.8 The thermodynamically stable pentavalent oxides are generally made from phosphines and arsines either with strong oxidants or activating with a transition metal, followed by oxidization by a less powerful reagent,9.14 Some preliminary results have been achieved with the use of triphenyl pnictogens as reductants. Y = P, As, Bi, and Sb Scheme 3.3. The oxidation with formation of pnictogen oxides for the reactions. The use of gallium nitrate was explored in oxidizing both triphenyl phosphine and arsine while concomitantly producing a Gal3" nanocluster. Allowing a solution of gallium nitrate and triphenyl phosphine to incubate at room temperature for 5 days resulted in isolation of only the starting materials. Only after heating for one to two complex which contains a hydrogen bond between two triphenyl arsenic oxides entities. This complex contains a [N03] counter ion, as oppossed compared to other previously formed clusters. 15-18 A P~P+ N03- species was also crystallized. Triphenyl phosphine can also be oxidized by Fe(N03)3 but it appears that the analogous Fel3 cluster is not formed; instead, a Fe(N03)2 (Ph3PO)3 salt is formed. A control reaction run without metal salts showed no oxidization of the pnictogens. 48 oc~ QQ~-A ~ OAi,-:Y ~ A+~ O P, \.0 ~PbG)'o~AS-o I '0 A ~,ij V . fj_~ .0 N03" 0 N03 Figure 3.5. The isolated products from the pnictogen oxidation. Although the preliminary results for non-nitroso reductants are encouraging, it is problematic that the Gal3 0 cluster was not isolated in addition to the organic reagent nor was any other multiple metal complex, Figure 3.5. A balanced equation cannot be written; therefore, this reaction is not useful to the project until a new inorganic product can be isolated. There is a solved crystal structure of the triphenyl arsenic oxide dimer and the tetraphenyl phosphine cation, but only IR confirmation of the triphenyl phosphine oxide. This set of experiments needs to be repeated because a metal product could not be isolated, not even as the starting salt, which is important to demonstrate the generality of the reaction for forming M13° clusters. A functional group of great interest was oximes because they tautomerize to nitroso functionality, but the tautomerization equilibrium lies heavily to the oxime isomer, Scheme 3.4. This tautomerization is not possible for nitrosobenzene because the a carbon is tied up in the aromatic ring and fully substituted. Unfortunately, the oxime reactions only yielded the recrystallization of the starting materials, with no nanoc1uster formation. 49 """" oxime Nitroso Scheme 3.4. Oxime-Nitroso tautomerization We preformed a series of experiments of the group 13 metals (AI, Ga and In) with DBNA at different pH's by adding KOH or HN03• Not surprisingly the yields of cluster were lower with decreased pH by addition of HN03 addition because we were driving the reaction the wrong way with addition of the nitrate anion. The yield of the reaction did not improve when the acid was changed to Hel. Only the addition of base had a positive outcome for the aluminum; the isolation of the flat A113 °cluster. We have not yet been able to isolate the isostructural flat In13 0 from any of these reactions. The large ionic radius of indium might prevent the formation of the cubic closed packed array of the Anderson core. In the following chapter I describe the current syntheses of the flat AI13 ° cluster using different bases. Treatment of aluminum nitrate with an organic nitroso-containing compound in good yields on a preparative scale under ambient conditions. Synthetic procedures yielding two different single crystal forms of the AlB0 cation with two varying counterion compositions are described. Aluminum is the third most abundant element and the most abundant metal in the earth's crust, found in many minerals and ores. Aluminum complexes are widespread in our environment, occurring in natural waters and clays usually as hydrated salts or clusters containing multiple aluminum ions held together through various bridging 50 groups.6, 7, 19-26 Despite the widespread prevalence of natural aqueous aluminum oligomers, relatively few have been synthesized on preparative scale and analyzed by single crystal X-ray diffraction.6 Furthermore, existing syntheses ofmany of these inorganic aqueous clusters suffer from long reaction times and/or poor yields (in cases where yields have been reported), hampering efforts to study the applications and bulk properties of these materials. 6,23-27 Herein we report facile syntheses that yield bulk­ scale single crystals of inorganic AI13(f.!3-0HMf.!2-0H)18(H20)2415+ clusters with various counter-anions (Scheme 3.5). Oligomeric aluminum clusters are found in two general structure types: 1) structures similar to the e-Keggin tridecameric clusters composed of a central tetrahedral metal ion surrounded by edge-shared octahedral AI06 units;21, 28-30 and 2) clusters comprised entirely of octahedrally coordinated Al cations (such as "flat"-AIl3°, Figure 3.6). Only a few reports of the latter class of clusters exist. 6,23-27 We report the synthesis of the purely inorganic salt AI13(f.!3-0H)6(f.!2-0H)18(H20bCN0 3)15 (AIl3°), a member of the latter class. The synthesis of purely inorganic aluminum salts has been reported as difficult and often elusive:6 the synthesis reported herein proceeds in reasonable isolated yields under ambient conditions and in preparative scales in a manner similar to the route we reported recently for the Gal30 congener. 51 A 24 <}-NO 13 Al(N03h + ----------..~ 1.3 eq KOH MeOH 47% B 24~N~ I NO 1.3 eq KOH MeOH 60% 24DBNA 1 drop NH40H MeOH 15% 24 DBNA 1.3 eq Al(OHh MeOH 15% Scheme 3.5 Synthesis of "flat" AIl30 nanocluster using the organic reductants nitrosobenzene (A) or N-nitroso-di-n-butylamine (B). The average Al-(~3-0), Al-(~2-0) and AI-O(H20) distances (A) are 1.879(7), 1.850(9), 1.917(15) and 1.877(6), 1.848(5), 1.92(2), respectively, in 1 and 2. Base = KOH, NH40H, or Al(OH)3 (Note: in the case of Al(OH)3, the use of 1.3 eq of base necessitates only an additional 11.7 eq of Al(N03)).)" . Synthesis of [Alu (P,·OHM'I·OH),.(H,O)14](NO,)" (1, route B). Aluminum nitrate nonahydrate (0.25 g. 0.667 rnmol. 13 eq) was dissolved in 2.5 mL of MeOH and N-nitroso-di-n-butylamine (0.34 g. 2.17 mmol, 42 eq) was added via asyringe. 2.5 mL of a 0.18M KOH solution in MeOH was then added to make a 0.09 Msolution. This solution was thoroughly mixed and left 52 Two recent syntheses of the "flat" Ga13° Keggin-like structure GaI3(1J.3-0HMfl2­ OH)18(H20h4(N03)15 were independently reported using gallium nitrate and an organic additive such as nitrosobenzenel or cucurbit[6]uril (CB[6]).31 A related AI13° core structure has been reported previously: both a structure supported by exogenous aminocarboxylate ligands and the inorganic chloride salt are known.25,26 However, the synthesis of the chloride salt suffers from a four and a half month preparation and only data on a single crystal were reported. Therefore, we sought to apply our synthetic strategy using nitroso organic compounds to prepare the analogous AI13° structures. We have previously shown the simple conversion of Ga(N03)3 into the flat-Ga13° nanocluster proceeds in the presence of nitrosobenzene. In this reaction, nitrosobenzene is believed to act as a scavenger for the nitrate counter-ions, in effect forcing the Ga3 + cations to form a higher nuclearity species. The stoichiometry for the process involves reaction of 13 eq Ga(N03h with 24 eq of nitrosobenzene to prepare one eq of Ga13° in gram quantities and up to 65% yield. 1 Modification of this method to form the related tridecameric aluminum cluster involves a key modification (Scheme 3.4): The reaction to form AI13°requires the addition of 1.3 eq of base, presumably a result of the increased pKa of hydrated aluminum complexes over gallium.32t Single crystals ofAI13° were isolated in un-optimized yields of up to 47% in under two weeks from a methanolic uncapped in a scintillation vial to evaporate over the course of 6-10 days. The remaining N-nitroso-di-n-butylamine was then removed via a syringe and the solution was washed with EtOAc (3 X 4mL), yielding a mixture of KNO, powder and single crystals of AI,,·. Crystals of 1 fonn in 60% yield with respect to aluminum nitrate. Alternate bases also effect the same transformation: NH40H (0.1 eq per eq of AI(NO,),) provides aslightly different crystal form of the cluster (2) in 15% yield; while 1.3 eq Al(OH), combined with 11.7 eq of Al(NO,), provide AI13 in 15% yield.t Synthesis of [AI,3(P3.0HMp·OH)18(H20)",](N03),s (1, route A). Methanolic solutions of aluminum nitrate nonahydrate (0.50 g, 1.33 mmol, 13 eq in 5mL MeOH) and nitrosobenzene (0.303 g, 2.82 mmol, 24 eq in 5mL MeOH) were mixed together and 1.3 eq KOH was added. The mixture evaporated slowly at room temperature over 4-8 days in ascintillation vial covered with tissue paper, yielding adark thick oil embedded with large single crystals of 1, which were isolated in 47% yield (with respect to aluminum nitrate). 53 solution of aluminum(III) nitrate nonahydrate, KOH and nitrosobenzene. A similar procedure using N-di-n-butylnitrosamine also affords AIl3° in reasonable yields (15-60%, depending on the base), and provides for a far easier workup, as crystals are isolated from the remaining liquid nitrosoamine rather than the tarry sludge left over from the nitrosobenzene procedure. We have also found that this nitrosoamine provides higher yields of the related Gal30 complex as well as a series of related mixed-metal clusters, all of which can be isolated in gram quantities. 33 A drawback to the use of KOH as the base in this procedure is isolation ofpure AIl3 0 from the powdery KN03 that presumably forms in the reaction as well. To avoid this time-consuming workup, we have successfully employed AI(OH)3, Nli40H, and NB\40H as alternate bases; all the salts that form as byproducts are soluble in the final oily mixture from which the AIl3° crystals are collected (Route B, Scheme 3.5). The single crystal X-ray structure of the "flat"-All3o cluster reveals a planar 34 centrosymmetrical Anderson_type ,35 AI(!l3-0H)6AI6(!l2-0H)6 core fragment surrounded by six aluminum ions.* The outer six aluminum cations alternate above and * xray X-ray diffraction experiments were carried out on a Bruker Smart Apex diffractometer at 153 K (1) and 173 K (2) K using MoKa radiation (1=0.71070 A). Absorption corrections were applied by SADABS. The structures were solved by direct methods, completed by subsequent difference Fourier syntheses, and refined by full matrix least squares procedures on P'. Highly disordered NO, anions and solvent water molecules in the crystal structure of 1 were treated by SQUEEZE,".. Correction of the X-ray data by SQUEEZE is 353 electron/cell; the calculated value for these nine NO, anions and seven water molecules in 1 is 349 electron/cell. All non-hydrogen atoms were refined with anisotropic thermal parameters. H atoms in 1 were found on the difference F-map and refined with isotropic thermal parameters. Some of the H atoms in the coordinated water molecules in 1 are disordered over three positions due to their involvement in three different H-bonds, and they were refined with occupation factor 1'=0.66. H atoms in 2 were not found and have not been taken into consideration. There is also a partial occupancy NH.+ cation in 2 on a special position 20(1)]: RI = 0.0479, wR2 = 0.1267, GOF = 1.069. Crystal data for 2: H"AI"N170 I06, M,=2381.68, colorless block, 0.08 x 0.08 x 0.05 mm, Triclinic, space group P-I (no.2), a = 12.623(3), b = 13.251(3), C = 13.597(3) A, IX = 74.877(4), fJ = 72.419(4), Y= 86.790(4)", V = 2092.4(2) J,,', Z = I, r"kd = 1.890 g/cm", l' = 0.326 mm", F(OOO) = 1232,26=, = 50.0°, 15065 reflections collected, 7308 unique [Rio! = 0.0700], R indices [1>20(1)]: RI = 0.0836, wR2 = 0.1961, GOF = 1.051. 54 below the planar core defined by the central 7 metal ions, and they are coordinated by four terminal aquo ligands. Two ~-bridging hydroxide ligands connect each of these Al(H20)4 fragments to each other and to the central core. 1,19,25,26 Two different single crystal forms were obtained from the syntheses; however, the cluster cations are nearly identical (see bond lengths in Scheme 3.4 and Supporting Information). Synthetic routes A and B (base == KOH or Al(OH)3) both provide structure 1 (AI13e9(H20)), whereas route B (base == NH40H) provides structure 2 (AlBe(N03)(N~)(H20)1O), which has an extra nitrate and ammonium counter-ion. The AI13° polycations determined in this work have a similar structure to the Ga130 cluster cation in which all the metal centers are octahedral (Figure 1A).1,31 In the crystal structures, both the AlB0 clusters are centrosymmetric in contrast to the 3 crystallographic symmetry of the Ga13 cluster cation, although the idealized symmetry of the AI130 clusters cations is close to 3. In 1 the AlB0 clusters are surrounded by N03­ anions and solvent water molecules forming O-H""O hydrogen bonds. In the case of the crystals grown from the reaction using N~OH as base, one molecule ofNH/ also co­ crystallizes, necessitating the presence of an extra N03- counter-ion (16 total) for charge balance. The hydrogen atoms of both the coordinating water molecules and those of the bridging I-l-OH ligands are involved in numerous intermolecular H-bonds. Similar hydrogen bonding is observed between clusters in Ga130 as well. 55 A B Figure 3.6 A) Polyhedral representation of "flat" M13 Keggin-like nanoclusters; B) Polyhedral representation of e-Keggin M 13 t structure-type comprising 12 octahedral metal centers (blue) that share vertices with a central tetrahedral (purple) metal center. Our method has allowed for the facile synthesis of AII30 clusters showing the generality of our strategy for preparing inorganic nanoclusters. A procedure for synthesizing preparative amounts of clusters of this type may have utility to researchers in the field trying to use these clusters as discrete molecular mimics of minerals or as single source precursors for thin film oxide materials. 6, 21 56 Supporting Information Available. X-ray data and details of X-ray diffraction studies in elF format, powder XRD and TGA data on All3. This material is available free of charge via the Internet at http://pubs.acs.org. 57 CHAPTER IV NOVEL HETEROMETALLIC TRIDECAMERIC INORGANIC NANOCLUSTER The synthetic procedure in this chapter was developed by a number of lab members including Jason T. Gatlin and Zachary L. Mensinger. Zachary L. Mensinger contributed substantially to this chapter by participating in the development of a standard synthetic procedure. I was the primary contributor to the optimization of the synthetic conditions and developed the purification procedure. Dr. Lev N. Zakharov was helpful in solving the crystal structures. Stephen T. Meyers and Dr. Prof. Douglas A. Keszler were helpful in the VT PXRD characterization of the clusters. Stephen T. Meyers and Dr. Prof. Douglas A. Keszler also used the tridecameric clusters as synthons for the synthesis of the think film oxides. This work has not yet been published but will be submitted to the journal Angewandte Chemie International Edition. Zachary L. Mensinger initially identified the alternate nitroso reductant for cluster synthesis, which yields the identical cluster to the Nitrosobenzene synthesis. Dr. Prof. Darren W. Johnson was the principle investigator for this work. 58 The following chapter discusses the inorganic side of the tridecameric cluster formation. This bridge and the following chapter detail new research into heterometallic tridecameric nanoclusters. Modifications of the Ga l3" synthesis via a slight change in the reaction pH allowed for the synthesis of the previously known analogous flat AI l3" inorganic nanocluster. An alternate reductant was discovered that delivers both the Ga l3" and the AI13" clusters in higher yields; this is presumably because of the ease of isolation. There are numerous examples of mixed metal Keggin clusters of the ratio M04(M'06)12, where M is the central tetrahedral metal and all the peripheral metal centers are octahedral. The previously know flat M13 °clusters, AIJ3°and Ga130, have all been homometallic and the question raised is whether other flat Ml3, both homo- and heterometallic clusters besides the previously known AI130 1,2 and GaJ303,4 clusters be synthesized in the same manner. Searches of the literature have yielded no reported synthesis of heterometallic flat M l3 °clusters. 24 Of'!, --- ------- -- ---- _Q_- ---­ CH30H, evaporation AI, Ga, In, Ph Ag, Ni, Co, Cu, Zn, Fe, St, Y Gd, Ce, Dy, Er, La, Nd, Sm Scheme 4.1. Mixed group binary Metal combinations. Multiple combinations and ratios of metals were used in an attempt to synthesize new heterometallic M l3°clusters. In an attempt to determine the generality of this new 59 found reaction, over one hundred binary combinations of commercially available metal nitrate salts were combined with stoichiometric amounts of the original reductant nitrosobenzene in methanol and allowed to evaporate in the same manner as the original cluster formation. A major problem with the reaction set is that the organic additive of nitrosobenzene yields a very viscus dark oil. When these experiments were run, the new alternate reductant of DBNA had not yet been discovered. The vast majority of crystals screened using nitrosobenzene yielded only starting materials. In addition to mixing metals from groups a series of experiments was to set up that only contained group 13 metals with a 1:12 ratio of metal salts (Table 3.2.1), in the hope that the substitution would occur only at the central location. Table 4.1. Ratios of the mixed group 13 cluster synthesis Al Ga In 1 1 1 1 1 1 1 12 12 1 12 1 1 12 1 12 12 1 A series of new tridecameric heterometallic GalIn clusters were synthesized by varying the starting ratio of Ga(N03)3 and In(N03)3 salts (Scheme 4.1). An n:m ratio of obtained when the n:m ratio was 1:6, and a n:m ratio of 7:6 afforded GaloIn3°' Symmetry of the Ga7In6° cluster cation is "3 which is analogous flat Ga130 and flat AI13° nanoclusters.4,5 All of the heterometallic clusters are isostructural with Ga13o. They 60 posess the same Gal(!-t3-0H)6Ga6(!-t2-0H)6 core, but vary in the gallium or indium atoms forming the third M-shell of the cluster (Figure 4.1). Unfortunately, there is no quick way to screen the crystal composition aside from collecting full XRD data sets. Bond distances and electron count allow for identification of the clusters (all clusters are similar, but possess different disorder in GalIn - See Supplemental). This could be used as a predictive strategy for the formation of other heterometallic clusters. Table 4.2. Starting material ratios compared to XRD and EPMA data of crystals. Starting Material Characterization XRD EA EPMA Gallium Indium Gallium Indium Gallium Indium Gallium Indium GaB 13 0 13 0 13 0 Ga12In 5 1 12 1 12 1 12 1 GallInZ 2 1 11 2 11 2 11 2 GaloIn) 7 6 10 3 9 4 10 3 Ga9In4 1 2 9 4 GaaIns 2 11 8 5 Ga7In6 1 12 7 6 6 7 6 7 The addition of acid did not yield new clusters, as the N03- anion was used up and the starting metal salts were able to recrystalize back. The crystal structures and starting material ratios were successfully used to form a predictive method for future heterometallic clusters. -- 61 14 -----_ .._-------- _._­ Number of GalliUln~in Starting Material versus Crystal S e ~ ! '" 4 ..'"~ z'" 2 01 , , , 0 2 6 8 10 12 j 12 -5 '0 ]j 10 ~ ~ J:: ~ II 8 .5 g Number or gallium aloms iu starting maleriat (oUI or 13) Graph 4.1. Plot of gallium numbers in crystal product versus starting material Unfortunately, heterometallic and homometallic clusters of metals other than those from group 13 have not been obtained. Currently success with these experiments has centered on heterometallic group 13 metals of just AI, Ga and In metal centers. A few data points have been successful in predictively making all seven in the series from Ga130 to Ga7In6°, Figure 4.2. However there has been no observable indium substitution in the inner core. We theorize that it is related to the large ionic radius of the indium cation. Future work will need to explore the potential to incorporate other metals from other groups into the nanoclusters, as well as fmishing out the mixed metal Group 13 series in both the gallium:indium and the aluminum:indium series. In addition to the mixed gallium and indium clusters, an analogous A1slnso tridecameric nanocluster was also successfully synthesized. 14 62 Gal1ln. Ga'01n3 Gagln. Figure 4.1. Gallium and Indium Heterometallic nanocluster series, with distribution. After isolation of Ga13° and AlB0 using DBNA, further experiments were carried out using the alternative reductant. This made screening for new crystals much easier, since the presence of crystals could easily be seen without magnification. Since decanting the oil formed as a byproduct made isolating the remaining crystalline product easy. There was less hunting in the organic residue for crystals. Figure 4.2. The heterometallic A1s1nso cluster, synthesized by Z.L.M. Surface chemistry of our nanoclusters by SEM and EPMA is being explored and will be discussed in Chapter V. In the following chapter the first synthesis of the heterometallic Ga7In6° nanocluster is discussed. A potential use for these clusters is in 63 thin film oxides. This will be explored as part of a collaboration with the Keszler group at Oregon State University. Our research has focused on inorganic metal-hydroxo nanoclusters of group 13 metals, such as our recently reported Gal3(~-OHMIlz-OH)18(H20)2iN03)15(flat-Ga130) cluster (this structure was independently isolated and reported by Fedin, et al.).6 The M(~-OH)6M6(1lz-0H)6 central fragment of this cluster forms a planar core with six additional M(H20)4 groups bound to the core via two 1lz-0H bridges each. The outer metal ions occupy alternate positions above and below the plane formed by the central seven metal ions. Metal complexes of this class are fairly rare, and typically consist of aluminum!' 7, 8, though several gallium complexes have recently been reported as well (ours, Fedin, Heath). Inorganic-only and ligand-supported clusters have been synthesized, with the latter generally being more common. One aspect that has been notably absent so far in this class is mixing of metal compositions within the same molecule, as well as clusters containing indium. Mixed-metal clusters are well known for other metal-oxo-hydroxo and metal-oxo clusters, such as Keggin-AIl3 t and Anderson-type clusters, two classes of molecules that are related to our flat-Ml3°. In the case of Keggin tridecamers, the central tetrahedral metal can be substituted, forming compositions of M1AI12 (M = AI, Ga, or Ge have been conclusively demonstrated, with others suggested). 9-19 Extensive reports exist for substitution of the central metal in B-type Anderson clusters as well, affording clusters of general formula M(OH)6M06018"', (M = Mn2+, Fe2+, Fe3+, Co2+, C03+, Ni2+, Cu2+, Zn2+, A13+, Ga3+, Cr3+, Rh2+, and pe+ and n = 2 or 3) in addition to various tungstates. To the best of our knowledge however, no such larger 64 nuclearity mixed-metal metal-hydroxo clusters consisting of aluminum or gallium have been reported. 1 2 Figure 4.3. 1 is Ga13(Jl3-0HMJl2-0H)18(H20)2iN03)15 and 2 Ga7I~(Jl3-0HMJl2­ OH)18(H20)24(N03)15 Prior synthetic preparation of this class of compounds has at times also proven quite difficult. Their synthesis often requires caustic or acidic conditions and high temperatures. Crystallization periods of months or even years are not uncommon. l , 7, 20 Due to these difficulties, relatively few metal-hydroxo clusters of aluminum and other group 13 metals have been synthesized, fewer still inorganic only clusters. An additional synthetic method for clusters of this class would be welcomed by researchers in the fields of environmental and geochemistry. Herein we report a previously unknown structure, gallium-indium structure. This cluster can be synthesized reliably in moderate yields utilizing our previously reported synthetic method, and in excellent yields with the use of a different nitroso compound, presented herein. 65 As an example, we have already begun exploring one application for theses clusters, driven by a rising interest in printed macroelectronics and the high carrier mobilities recently reported in disordered Group-13 and other p-block oxides. 21-23 Most solution precursors for printed oxide films involve controlled hydrolysis ofmetal-organic compounds and the condensation ofmetal-hydoxo "sols" which are then pyrolyzed to form the oxide. Such films are beset by a variety of density, defect, and segregation issues relating to the inhomogeneous nature of the sol and retention of significant organic components. From this perspective, soluble all-inorganic, heterometallic hydroxo­ clusters provide model oxide precursors driven by similar hydrolysis and condensation principles, but lacking detrimental organic moieties. In this contribution we report a previously unknown structure, Ga7In6()l3­ OH)6()l2-0H)IS(H20b(N03)15 (flat-Ga7In6)' consisting of a mixed-metal gallium-indium structure. This cluster can be synthesized reliably in moderate yields utilizing previously reported synthetic methods, and in excellent yields with the use of a different nitroso compound, presented herein. Finally, we describe the adaptation of these structures as precursor solutions for oxide semiconductor thin-films by fabricating high-performance thin-film transistors (TFTs) with spin-coated Ino.92GaI.OS03 channel layers. Our previous report describes the mild preparation of the inorganic flat-GaJ30 compound, prepared by dissolving Ga(N03)3 and nitrosobenzene in MeOH followed by slow evaporation. Crystals are then manually separated from the resultant black tar-like product mixture. Using this method, yields up to 65% of flat-Gal3 °could be obtained in small scale. This same procedure was applied to a mixture of Ga(N03)3 and In(N03)3 in a 66 1:12 ratio, which afforded a mixed-metal, flat-Ga7In6° cluster in 25% yield. Again, crystals were manually separated from the black product mixture. The prospect of mixed-metal clusters of this class has not been addressed to our knowledge. NO "Ga13" 1: n =13, m =0; 65% ~ "G."o." ,,, -1, m -12; 25% n Ga(N03h m In(N03h MeOH __________ "Ga13" 1: n =13, m =0; 85% ~ "Ga7In6" 2 n =1, m = 12; 94% ~N~ I NO Scheme 4.2. Redox reaction forming Ga13 ° and heterometallic clusters. Scheme 4.2 depicts the synthetic route to structures 1 and 2 using two different nitroso compounds. Symmetry of the flat-Ga7In6°cluster cation is 3" as with the analogous flat-Ga13o cluster.4 Compound 2 is isostructural with 1, possessing the same Ga(1-l3-0H)6G~(I-tz-OH)6 core, but varies with indium atoms forming the third M-shell in the cluster connected via I-tz-OH bridges (Figure 4.2). We have also conducted experiments aimed at controlling the ratio of Ga:In present in these mixed-metal clusters, and these results will be presented in a future publication. Unfortunately, there is currently no quick way to screen the crystal composition aside from collecting full XRD data sets, where bond distances and electron count allow for identification of the clusters. Surface chemistry by SEM and EPMA are being explored. To address the problems of difficult isolation and limited reaction scale, we sought alternative nitroso compounds to nitrosobenzene. The most successful so far has been N-nitroso-di-n-butylamine. This compound is a slightly yellow viscous liquid with low vapor pressure. Use of this alternative nitroso compound affords clusters 1 and 2 in 67 superior yields, 85% and 95% respectively. The yields are likely increased in part because the reaction with N-nitroso-di-n-butylamine produces a mixture that is a transparent oil instead of the viscous black tar found in the reaction with nitrosobenzene. The solid crystalline product is thus easier to isolate from the reaction with N-nitroso-di­ n-butylamine. N-nitroso-di-n-butylamine is removed via syringe, and the remaining crystals are washed with cold EtOAc (three times) and dried. N-nitroso-di-n-butylamine allows preparation of compounds 1 and 2 in gram scale quantities. All-inorganic hydroxocation condensation routes to dense, high-quality oxide dielectric films have been lately demonstrated24,25 Based on these results, the discrete hydroxo clusters 1 and 2 were immediately recognized as potential oxide precursors operating on similar principles. Cluster 2 is ofparticular interest due to the large indium fraction and the excellent performance of In203-based semiconductors. Thin Film Transistors with amorphous Ino.92GaI.OS03 (IGO) channels derived from spin-coated aqueous solutions of 2 will be described more fully in a forthcoming publication, though preliminary device characteristics are presented in Figure 4.4. Von for the device shown is, -6 V while on-to off current ratios are > 106 on thermally grown Si02 dielectrics. Field-effect mobilities for these bottom-gate devices are ~ 9 cm2V· l S·l after annealing to 600°C. The direct deposition of such high-performance semiconductors from aqueous solutions is unprecedented, and an important step towards printed macroelectronics. 10.;\ vos 30 V W/L= 17 10"" L=86 m 10-6 --­« --­ 10-0 10-7 10-8 10 :2 117 116 .n,. ,,. "', 22.1 1!'. [1,1 ..... '.\4.1 OIl'73 ""A 1M /1I.9 16J-l 'MOA ;19.1 47.7 10',.. 141.1 J21J 4:)4,9 1911o ,,. 1'2.1 <0O 139.1 9810 g;g,6 "". &19.5 -;S1A 'S1.1 IJ.6 Vl § Vl (JQ (1) CD 'U (1) ~ P> Vl Vl ciQ' ~ (1) g ~ to CI ~ P> Vl is- to to to ~ m 0) 9238 -69Ga03 J 16 .9271 -69Ga02(OH), 11' ? 8.922 -71GaO:J 9262 ­71 Ga0;z(OH)1 9338 -(J9Ga (OH~ 8.9305. 69GaOI(OH~ II 11 Jl9 119 p;;::­ 929 -11 GaIO, (OH>Z 9416 ­69Ga(0I-T1(HzO)1 120 120. 913 -69Ga(OH~ (Hz0>Z J21. 9573 ­69Ga(Hz0)3 122 >­ I 24.9564 -71 Ga(H20)3 ~ 6L 80 When the mass and element are entered, a mass spectrum fragment calculator finds potential fragments that fit that stoichiometry. This calculator as well as most simple general chemistry calculators (that is, not part of a MS instrumentation package) do not take into account the isotopes of elements as seen, Figure 5.06. They only use the average mass, which means that no single peak can be entered in for its isotope clustering; only the middle or most intense peak is the target. This is where the real data is much more complicated than the simulated data without isotopes included. However, the same iMass program is able to show isotope distribution for a given molecular formula, Figure 5.08b. There appears to be a long range "AB: pattern, which could correlate to GaO and Ga02 additions to the previous cluster. Figure 5.07 shows a section of the ToF-SIMS spectra of compound 1 with an enlargement of the peaks clustered around 495 Daltons. This shows the interdigitated patterns as well as other small peaks that may be multiply-charged species. 81 A Mass/z Figure 5.07. Mass spectrum of 1 from 550 to 1000 Daltons With the aid of computer programs, data analysis has become much easier. There are programs used for protein characterization that use the spacing between the peaks to determine the charge of the fragments and, therefore, the mass of the parent ion. There are two ways of manually analyzing the data, either the plug and chug method of entering the mass and finding corresponding compounds via the commercially available mass spec fragment calculator, or plugging in chemically reasonable formulae and determining their mass. Both of these involve trial and error, but they do provide a good starting point. Alternately, the isotope distribution can be used to help determine a starting point with the ratios of the peaks revealing the number of gallium centers contained in each fragment. The difference is building up from the bottom or taking a top-down approach to peak assignment. The expanded section of Figure 5.07B is shown again in Figure 490.0 493.0 491J.O 82 5.08A and the two interdigitated patterns that are offset by a single proton are color- coded. The red spectrum in A is very similar to the predicted pattern seen in B. B 10000'A I 16.00 2 5000 ~ 2~.OO 490 500 ! i Figure 5.08. Expansion of Spectra 1 at 495 Daltons corresponding to a Gas07(OH)2 fragment A series of stable fragments were expected to be present, one of which was the Anderson-Evans core ofM7. The Anderson-Evans fragment was not observed. However, it was observed that there are other existing multiple metal clusters that could be potential fragments of a tridecameric cluster. There are two known Mg clusters that are similar to the core of the M 13 cluster. 10,11 The physical difference between the two clusters involves the removal of one of the inner ring metal centers. This allows the two adjacent metals to bend out of the plane, relieving torsional strain. The remaining four metals are still planar as seen in Figure 5.09. If one outer metal is removed, and the structure is minimized and compared to the corresponding formula for the Anderson- Evans M7cluster, there is a large difference in minimized energies, with approximately 30 kcaVmol stabilizing energy for the Anderson-Evans cluster as determined by CAChe using the MM3 force field. 12 83 Figure 5.09. Stable M7 POM fragments Data that appears to be missing from the table is actually the result of peaks that are too small to resolve out the noise. This is where the isotope pattern has now provided diminishing returns, and where the smaller cluster that is made up exclusively of the lower isotope is very difficult to identify. ToF-SIMS is a highly energetic environment where electrons are easily transferred to the matrix and other fragments during flight, 19where actual fragments may not match expected ones. 13- Based on this data we can start to assign structures to the peaks that we see. Figure 5.10 represents what we believe the fragments to be. This data assignment will help identify more peaks in the set and should be applicable to the heterometallic clusters 2-7. . . . . . . . . . . . . . . . . . . . . . ' :. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . • . . . . ~ 2. 5­ c: ~ c: 2. 0 1. 5 Fi gu re 5 .1 0. L on g ra n ge s pe ct ru m o f 1 w ith c lu st er a ss ig nm en ts. 00 . j:::. . 85 Figure 5.11. Clusters that fit peak identification for spectrum of 1 Table 5.3. High Nuc1earity species Peak assignments Error Error Fonnula Calculated Observed (Dalton) (ppm) 69GaSOg(OH)1 489.6258 489.5665 -0.0593 121 69Ga47lGajOg(OH), 491.6250 491.5682 -0.0568 115 69Ga371GazOg(OH)1 493.6241 493.5659 -0.0582 118 69Gaz7lGa30s(OH)1 495.6232 495.5643 -0.0589 119 69Ga17IG~Os(OH)1 497.6223 497.5663 -0.0560 113 69G~09(OH)1 574.5508 574.4926 -0.0582 101 69Gas71GaI09(OH)1 576.5499 576.4900 -0.0599 104 69Ga41lGaZ09(OH)1 578.5491 578.4900 -0.0591 102 69Ga371Ga309(OH)1 580.5482 580.4900 -0.0582 100 69Gaz7IG~09(OH)1 582.5473 582.4900 -0.0573 98 69GaI71Gas09(OH)1 584.5464 584.4900 -0.0564 97 Conclusions We have shown that TOF-SIMS has the potential to be used for the characterization of polyoxometalates. While still not a fully developed method, it does show an increased potential for this technique in other characterizations ofmaterials, and in some peak isolation and identification that can be adapted to other species. The first step is to try to apply these results to compound 7, which has a complete substitution of the outer ring. This data shows that there are stable fragments in the gas phase. Previously this has been a concern. This new data could open the door for the use of 86 these clusters as synthons in a CVD or PVD method of film preparation, not just in the SILAR method that has been utilized thus far. 2o, 21 Future Works Work continues on the calibration curve for additional peak assignments. The lessons learned here should next be applied to the compound 7. In the future we should also screen the analogous AI13 cluster using TOP-SIMS. The aluminum data will be useful for two reasons: the analogous cluster should yield very similar if not the same fragments, and the lack of isotopes should simplify the spectra with fewer peaks, helping improve the signal to noise ratio of the data. The slightly smaller ionic radii of aluminum may make the cluster more stable. Core fragments that are identified and predicted for the Ga samples should be able to be seen in heterometallic clusters. Organic ligands such as HEIDI may allow for large fragments to be seen because of stability imparted to the cluster by the ligand. Working up the existing data with other programs would help with pattern identification. 22 Recent observations should allow for fragment predictions to be applied to some of the heterometallic clusters starting with 7. The same clusters can be continued to be screened using other MS instruments, MALDI would be a prime starting point. A parallel study should be to screen the ToP-SIMS of the known Gag and Aig clusters, in order to test if they are indeed viable fragments of the Anderson-Evans core. Tof-SIMS has the potential to be used as much more than just an elemental analysis technique. The different heterometallic clusters in the series could help provide very useful data on the labiality of different metal bonds in analogous clusters under similar 87 conditions. Once we have finished with the gallium indium series we could use it as a base for the aluminum and indium series. 88 BRIDGE The fIrst fIve chapters of this thesis focused on inorganic oxo clusters. They include a small review, the synthesis, experiments, uses and characterization of tridecameric nanoclusters. Throughout these experiments there were numerous leads were not explored due to time constraints. The following chapter turns to a summary of the organic templated nanocages project that I researched for the fIrst year and a half in Dr. Johnson's laboratory. I conducted the research on templated nanocages with assistance from three undergraduate (Michael N. Gonsalves, Pratistha Ranjitkar and Jean-Michel Moreau) and two rotation students (Eric L. Spitler and Charles A. Johnson, Jr.). Dr. Prof. Darren W. Johnson was the principle investigator for this work. --------- 89 CHAPTER VI SUMMARY OF INORGANIC TEMPLATED NANOCAGES The goal of my original graduate research project was to create a rigid bis­ bidentate organic ligand that would bridge multiple metal centers allowing for the creation of an enclosed cavity. Two different classes of rigid bis-bidentate ligands were explored: first the pyridine-imine binding motif based on a known self-assembled tetrahedron synthesized by Yan I; and second, a pyridine-pyrazole binding motif based on other self-assembled clusters by Ward. 2-5 A third binding motif based on the work of Saalfrank6-9 was suggested and outlined but not yet tried. All of these ligands are modifications of previous ligands, with distal functionality built in to allow for the covalent coupling of the ligands into one nanocage templated by the four non-co-planar metals. metal-ligand nanocage !MoL'I" organic nanocage [L'] funclionaJize -----------. applications lc:mplate IM4Lt;J3t Scheme 6.1. The general scheme to use an ~L6 capsule as a template to form an organic nanocage, L'. The general M4L6 tetrahedron template strategy is depicted above (Scheme 6.1). Six equivalents of an appropriately designed ligand (blue Jines) are combined with four equivalents of metal (red pheres) to self-assemble a ~L6 tetrahedron (metal-ligand 90 nanocage template) related to the Zl14L68 + from the literature precedent. The next step is· a covalent capture by a cap (green) that binds all six ligands together to yield the MtL' complex. The final step of demetallation yields the organic nanocage, L'. This complex has a vohune that is defined by its covalently linked shelL The known appropriate crystal structures were imported into CAChelO with geometries locked. Then to the distal ends of the ligands carboxylic acids were added as handles for condensation with a three-fold symmetric compound. The overall structures were then minimized with a MM3 force field. In each case the propyl spacer of tris-(3­ arninopropyl)amine (TRPN) provided a better fit than the ethyl spacer of the tris-(2­ aminoethyl)amine (TREN). Pyridine-Imine Type Ligands The carboxylic acid derivative of the desired ligand was synthesized. The Yan procedure for crystallization of the tetrahedron was followed for the two different ester­ protected ligands (ethyl and benzyl) as well as the deprotected carboxylic acid. Synthesis of the ester-protected ligands was carried out despite some serious solubility issues regarding the benzyl ester once it was condensed with benzidine. The condensation product of the terphenyl spacer of the 4.4"-terphenyl-diarnine suffered from extremely poor solubility in various organic solvents. The deprotection of those ligands proved to be very difficult. The same condensation conditions did not work for other esters and spacer combinations, Scheme 6.2. In addition, there was a remarkable difference in the reactivity of the two different ester-protecting groups. 91 A second plan of attack was to try a capping-first strategy where the three-fold symmetric cap was first coupled to the 2-acyl-pyridine, then the pyridine was condensed to the rigid backbone spacer to form the imine. A series of two-fold symmetric backbones was explored, Scheme 6.3. This strategy allowed for the insertion ofdifferent rigid backbone scaffolds in a modular synthesis, Figure 6.1. Benzidine was the only diamine that was condensed with the acyl nicotinate and was still soluble for use as a ligand. The octofluoro version of benzidine did not condense with the 2-acyl pyridine. The p-terphenyl diamine did condense but was so insoluble that characterization of the deprotected product was almost impossible. Because of these difficulties, these two rigid spacers were not used, and work continued with the benzidine spacer. 92 o ~ H0 2 0 7'1 N>-.. N'" r r F metal-ligand nanocage I -& N'" template§~: 2 lM4L61s+~I OOV HOO Scheme 6.2. Deprotection of benzyl ester ligand and metal-ligand self-assembly. The benefit of a modular route allows for the order of reaction to be rearragned while reaching the same target. The capping-first strategy uses the same starting materials and even the same first reaction. But the deprotection happens second, as opposed to the condensation with the di-amine, in order to set up for the covalent capping. The 2-acylnicotinic acid as either the carboxylic acid or the activated ester could be coupled to the three-fold symmetric cap to yield the vertex 11. The product was formed in very low over-all yields. An alternate scheme (Scheme 6.3) was not completed which had the potential for an even lower yield where the low yielding acylation reaction would need to be run on the three pyridines, yielding the same multiple 93 o OH 0 Cl JX~ C)'CI JX~ l~-l~ I 95% C Ie products. The acylation reactions of the nicotinic esters proceed in low yield; the redeeming quality is the low cost of the reagents and the easy reaction conditions. If the same acylation were tried on 12, there would be a large mixture of products, and the increased bulk of the whole cap might help with the yield of the reaction, by favoring more acylation on the para position, making the difference between the two routes negligible. o ~--~o HHN\ H~N~ °2N~N~NYV R 0O~OH \f O~CI TRPN 9 "", 11 R Cl.... S'Cl "" .. "" N o "" I -- "" N wfoTEA 600 '-' 0 .til t:: Q) 400i:l - 200 o o 5 10 15 20 25 30 35 40 45 2 theta (deg) Figure Bl. X-ray powder diffraction pattern of a fresh sample of 1. 20 115 10000 8000 6000 4000 2000 o o 5 10 15 20 25 30 35 40 45 2 theta (deg) Figure B2. X-ray powder diffraction pattern calculated from the single crystal structure of1. - ~ g l"l ~ ~ a C'! ~ ~ ~ II II I I III I I~ Id~l" 1"11,,o 100 200 300 400 500 600 700 ml Figure B3. LC-MS trace of oily residue 116 Sample: ERO,O File: C:\TA'Dala\TGA\erO' 0.001 Size: 4,6140 mg TGA Operator: Eisebelh Rather Method: Polymer Decompos~ion Run Data: 2.Aug.Q4 14:06 L-..""II-or.::---+ '001 32.12~ (1.482mg)'\ 80 ­ '\ +.---------------+ ooi \ .. 24.74%\ (1.142mg)'~~ '" 2.017'4'~.______ (O.o9305mg) ~_.-._-_._---'I---...,=-----....... ~ ~ - • II I l I 20 -+--~--ri--~-.,.i--~-,.'-~--,-,----,-,----.,-~----jl1 o 100 200 300 400 500 600 700 Temperature (0G) UUJtrnl\0'2.5H TA lulnmo •• Figure B4. TGA of tridecameric inorganic nanoc1uster. JTG6 XRD Data The crystal was grown by evaporation from MeOH at 22 DC over 1 week. The crystal was mounted on a quartz fiber with paratone oil. Data in the frames corresponding to an arbitrary hemisphere of data (00 scans, 10 sec frames) were intergrated using SAINT.1 Data were corrected for Lorentz and polarization effects. The data were further analyzed using XPREP.2 An empirical absorption correction based on the measurement of redundant and equivalent reflections and an ellipsoidal model for the 117 absorption surface were applied using SADABS. 3 The structure solution and refinement were performed using SHELXTL (refined on F2). 2 All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were included but not refined on all appropriate atoms. Special positions for the nitros. Crystal size 0.45 x 0.25 x 0.15 mm; T = 21 DC; Rhombohedral, R-3 (#148), a = 20.214 (3) A, b = 20.214 (3) A, c = 18.353 (4) A, a = 900 , ~ =900 , y = 1200 ; V = 6494.7 (19) A3, Z = 3, Il = 4.128 mm-\ F(OOO) = 4116 pealed = 2.127 g mL-', 2E>max = 52.80 • Of the 12652 reflections that were collected, 2832 were unique (Rint = 0.0318); equivalent reflections were merged. Empirical absorption correction: Tmax = 0.999, Tmin = 0.660. Final R1 = 0.0404 for 2832 data for 1>20(1) (189 Parameters, 6 restraints); for all 2832 data, wR2 =0.1120, GOF = 1.153. 118 H H H~w Figure B.S. Crystal Structure of Ga 13 119 Table B.l Experimental Crystal data for Gal3 HnGal3N1S099 228 parameters Mr = 2773.09 H atoms treated by a mixture of independent Trigonal and constrained refinement R-3 a = 20.214 (3) °A Mo Ka radiation b = 20.214 (3) °A A. = 0.71073 A c=18.353(4)OA Cell parameters from? reflections a = 90.00 e = ?-? ° V = 6494.7 (19) °A3 v = 4.128 mm-1 Z=3 T= 293 (2) K Dx= 2.127 Mg m-3 Polyhedron Dmnot measured Colorless 0.3 x 0.2 x 0.2 mm Crystal source: ? Data collection Broker P4 diffractometer e max = 26.40° w scans h = -24 -> 25 Absorption correction: k=-25 ->25 SADABS 1= -22 -> 22 Tmin = 0.702, Tmax = 1.000 ? standard reflections every? reflections 12648 measured reflections intensity decay: ?% 2831 independent reflections 2500 reflections with w=lI[ 2(F/) + (O.07l6Pl + O.OOOOP] >2sigma(I) where P = (F/ + 2Fc 2)13 Rinl = 0.0320 (!J./a)max = 0.006 Apmax = 0.949 eN Refinement Apmin = -0.567 eN Refinement on F­ Extinction correction: none R[F2 > 2 (F-)] = 0.0310 Scattering factors from International Tables wR(F-) = 0.0988 for Crystallography (Vol. C) S = 1.035 2831 reflections Table B.2. Fractional atomic coordinates and equivalent isotropic displacement parameters (A2) Ucq = (113) ~i ~pijaiaiai.aj . Occupancy x Y z Ueq Gal 1 1.0000 1.0000 0.0000 0.0196 (2) Ga2 1 0.837137 (19) 0.980265 (18) -0.004021 (17) 0.01921 (13) Ga3 1 0.697660 (19) 0.821112 (19) 0.09437 (2) 0.02311 (14) 01 1 0.94201 (11) 1.03770 (11) -0.05420 (13) 0.0206 (5) 02 1 0.81260 (13) 0.88619 (12) -0.05055 (12) 0.0220 (5) 03 1 0.75336 (12) 0.92485 (12) 0.06121 (12) 0.0236 (5) 04 1 0.79718 (13) 1.02078 (13) -0.07527 (13) 0.0252 (5) 05 1 0.73030 (15) 0.85021 (15) 0.19711 (14) 0.0366 (6) 06 1 0.61213(14) 0.84161 (15) 0.11670 (16) 0.0383 (6) 07 1 0.62994 (14) 0.71683 (14) 0.13696 (15) 0.0361 (6) 08 1 0.64377 (14) 0.77510 (15) 0.00175 (14) 0.0351 (6) Nl 1 0.72277 (17) 0.79552 (17) 0.80145 (17) 0.0350 (7) 011 1 0.71311 (19) 0.74566 (17) 0.84609 (17) 0.0521 (8) 012 1 0.7779 (2) 0.85971 (19) 0.80506 (18) 0.0694 (11) 120 013 1 0.67501 (18) 0.77931 (17) 0.75176 (19) 0.0594 (9) N2 1 0.6356 (2) 0.7175(2) 0.3316 (2) 0.0496 (9) 021 1 0.6723 (2) 0.7530 (2) 0.38610 (19) 0.0617 (9) 022 1 0.5727 (3) 0.7093 (4) 0.3191 (3) 0.1118 (18) 023 1 0.6625 (2) 0.6879 (2) 0.28942 (19) 0.0620 (9) O1W 0.41 0.4695 (4) 0.7399 (5) 0.1144(7) 0.076 (3) 02W 0.36 0.4954 (6) 0.7571 (7) 0.2073 (7) 0.082 (4) N3 0040 0.8976 (12) 1.0014 (10) -0.2688 (9) 0.192 (11) 031 0.40 0.9191 (5) 1.0314 (5) -0.2036 (3) 0.0442 (18) 032 0.40 0.9065 (9) 0.9441 (10) -0.3005 (8) 0.130 (6) 033 0.40 0.8553 (12) 1.0232 (9) -0.3095 (14) 0045 (4) N3B 0.10 0.9278 (16) 0.9982 (17) -0.2055 (16) 0.098 (9) 031B 0.10 0.961 (2) 1.0686 (18) -0.200 (3) 0.098 (9) 032B 0.10 0.9634 (18) 0.964 (2) -0.206 (3) 0.098 (9) 033B 0.10 0.8571 (16) 0.962 (2) -0.211 (3) 0.098 (9) Table B.3. Anisotropic displacement parameters (A2) Ull U22 U33 Ul2 UB U23 Gal 0.0162 (3) 0.0162 (3) 0.0264 (4) 0.00809 (13) 0.000 0.000 Ga2 0.01709 (19) 0.01609 (19) 0.0241 (2) 0.00803 (13) 0.00043 (12) 0.00067 (12) Ga3 0.0208 (2) 0.0206 (2) 0.0277 (2) 0.01018 (15) 0.00380 (13) 0.00216 (13) 01 0.0203 (11) 0.0213 (11) 0.0225 (12) 0.0120 (9) 0.0009 (8) 0.0017 (8) 02 0.0259 (11) 0.0209 (10) 0.0225 (11) 0.0142 (9) -0.0053 (9) -0.0030 (8) 03 0.0240 (11) 0.0175 (10) 0.0283 (12) 0.0097 (9) 0.0062 (9) 0.0003 (9) 04 0.0210 (11) 0.0209 (11) 0.0318 (12) 0.0089 (9) -0.0063 (9) 0.0002 (9) 05 0.0380 (14) 0.0430 (15) 0.0317 (14) 0.0225 (12) -0.0004 (11) -0.0036 (11) 06 0.0324 (13) 0.0376 (15) 0.0508 (17) 0.0219 (12) 0.0112 (12) 0.0086 (12) 07 0.0364 (14) 0.0264 (12) 0.0404 (14) 0.0119 (11) 0.0075 (11) 0.0085 (11) 08 0.0359 (14) 0.0312 (13) 0.0349 (14) 0.0144 (11) -0.0055 (11) -0.0022 (11) Nl 0.0325 (16) 0.0331 (16) 0.0338 (17) 0.0121 (14) -0.0071 (13) -0.0049 (13) 011 0.0584(19) 0.0385(16) 0.0523(18) 0.0189(14) -0.0214 (15) 0.0058 (14) 012 0.066 (2) 0.0501 (19) 0.0422 (19) -0.0079 (17) -0.0183 (16) 0.0020 (15) 013 0.0482 (18) 0.0440 (17) 0.063 (2) 0.0058 (14) -0.0312 (16) 0.0119 (15) N2 0.059 (2) 0.062 (2) 0.040 (2) 0.040 (2) -0.0015 (17) -0.0036 (18) 021 0.086 (3) 0.073 (2) 0.0492 (19) 0.057 (2) -0.0072 (18) -0.0143 (17) 022 0.095 (3) 0.194 (6) 0.081 (3) 0.098 (4) -0.012 (3) -0.Q17 (4) 023 0.084 (3) 0.066 (2) 0.049 (2) 0.046 (2) -0.0035 (16) -0.0127 (17) 01 W 0.023 (4) 0.052 (5) 0.144 (10) 0.013 (3) -0.005 (5) 0.003 (5) 02W 0.055 (6) 0.076 (7) 0.114 (10) 0.032 (6) 0.045 (6) 0.039 (7) N3 0.18 (2) 0.133 (17) 0.24 (2) 0.060 (15) 0.122(18) 0.075 (17) 031 0.077 (5) 0.066 (5) 0.009 (3) 0.050 (4) 0.007 (3) -0.007 (3) 032 0.192(17) 0.152(14) 0.075(9) 0.108(13) 0.042 (9) 0.024 (8) 033 0.19 (2) 0.048 (9) 1.12 (11) 0.064 (12) 0.19 (4) -0.02 (3) Table B.4. Selected geometric parameters (A, 0) Gal-Ol i 1.959 (2) Ga2-Q2 1.910 (2) Gal-Olii 1.959 (2) Ga2-03 1.913 (2) Gal-O1iii 1.959 (2) Ga2-02iii 1.917 (2) Gal-Ol 1.959 (2) Ga2-04 1.922 (2) Gal-Ol iv 1.959 (2) Ga2-01 2.056 (2) Gal-Olv 1.959 (2) Ga2-01 v 2.153 (2) 121 Ga3-04v 1.913 (2) 02-Ga2-03 89.06 (9) Ga3-03 1.917 (2) 02-Ga2-02iii 164.25 (12) Ga3-08 1.982 (3) 03-Ga2-0iii 96.90 (9) Ga3-05 1.987 (3) 02-Ga2-04 99.49 (10) Ga3-07 2.011 (2) 03-Ga2-04 103.75 (10) Ga3-06 2.011 (2) 02iii-Ga2-04 93.26 (10) 01_Ga2iii 2.153 (2) 02-Ga2-01 92.47 (10) 02-Ga2v 1.917 (2) 03-Ga2-01 166.37 (9) 04--Ga3iii 1.913 (2) 02iii-Ga2-01 78.37 (9) N1-012 1.218 (4) 04--Ga2-01 89.37 (9) N1-011 1.236 (4) 02-Ga2-01v 76.16 (9) Nl-013 1.247 (4) 03-Ga2-01v 90.68 (9) N2-022 1.218 (5) Oiii-Ga2-01v 89.16 (9) N2-021 1.239 (5) 0~Ga2-01v 164.96 (10) N2-023 1.256 (5) 01-Ga2-01v 76.57 (12) 01W-02W 1.767 (18) 04v-Ga3-03 96.35 (10) N3-031 1.313 (15) 04v-Ga3-08 93.19 (11) N3-033 1.362 (16) 03-Ga3-08 97.20 (10) N3-032 1.386 (14) 04v-Ga3-05 93.08 (11) N3B-032B 1.2215 03-Ga3-05 92.92 (10) N3B-031B 1.2363 08-Ga3-05 167.43 (11) N3B-033B 1.2420 04v-Ga3-07 91.29 (10) N3B-032Biv 1.28 (6) 03-Ga3-07 171.86 (10) 031B-032Biv 1.26 (7) 08-Ga3-07 85.13 (11) 032B-031Bi 1.26 (5) 05-Ga3-07 83.84 (11) 032B-032Biv 1.27 (5) 04v-Ga3-06 177.38 (10) 032B-032Bi 1.27 (8) 03-Ga3-06 86.25 (10) 032B-N3Bi 1.28 (5) 08-Ga3-06 86.79 (12) 05-Ga3-06 86.45 (11) 01 i-Gal-01ii 83.50 (9) 07-Ga3-06 86.10 (11) 01 i-Ga1-01iii 180.00 (12) Ga1-01-Ga2 101.62 (10) 01 ii-Gal-01iii 96.50 (9) Ga1-01-Ga2iii 98.31 (10) 01i-Ga1-01 96.50 (9) Ga2-01-Ga2iii 95.47 (9) 01 ii-Gal-01 180.0 Ga2-02-Ga2v 108.99 (11) 01iii-Ga1_01 83.50 (9) Ga2-03-Ga3 134.68 (12) 01i-Ga1-01 iv 96.50 (9) Ga3iii-04--Ga2 130.90 (12) 01ii-Gal-01iv 83.50 (9) 012-Nl-011 121.3 (3) 01iii_Gal-01iv 83.50 (9) 012-N1-013 119.7 (3) 01-Ga1-01 iv 96.50 (9) o11-N1-013 119.0 (3) 01 i-Ga1-01v 83.50 (9) 022-N2-021 120.8 (4) 01 ii-Gal-01v 96.50 (9) 022-N2-023 119.4 (5) 01 iii-Ga1-01v 96.50 (9) 021-N2-023 119.8 (4) 01-Ga1-01v 83.50 (9) 031-N3-033 117.9 (12) 01 iv-Gal-01v 180.0 031-N3-032 128.1 (13) 122 033-N3-032 113.8 (11) N3B-032B-032Biv 61 (3) 032B-N3B-031B 121.1 031Bi-032B-032Biv 174 (3) 032B-N3B-033B 119.7 N3B-032B-032B i 121 (3) 031B-N3B-033B 119.2 031Bi-032B-032Bi 116 (4) 032B-N3B-032Biv 61 (3) 032Biv-032B-032Bi 60.0 031B-N3B-032Biv 60 (3) N3B-032B-N3B i 179 (4) 033B-N3B-032Biv 175.2 (7) 031Bi-032B-N3Bi 58 (3) N3B-031B-032Biv 61 (2) 032Biv-032B-N3Bi 117 (2) N3B-032B-031B i 123 (4) 032B i-032B-N3Bi 57 (2) Symmetry codes: (i) 2-y, 1+x-y, z; (ii) 2-x, 2-y,-z; (iii) y, 1-x+y,-z; (iv) 1-x+y, 2-x, z; (v) 1 +x - y, X,-z. We are exploring the generality of the nitroso oxidation reaction to see if other inorganic nanoc1usters can be synthesized via the same method and if there are other possible oganic reductants that can be used to make the same type of clusters. Follow up work on making new clusters, trying other reductants and checking their functional group tolerance. After publication in the Journal of the American Chemical Society our results were highlighted in the March 4th issue of Science as an Editor's choice. 123 HICiHLICHT OF THE RECENT LITERAfU E EDITORS' CHOICE "dlt"d by Gilb"rt Chin prall ate the orllanizdt on of CG ~nsed ,1uc[eat chromo-.:e'lIeI'S. ­ OC (~'Q ~}.' CHEMISTRY t nd Accurate 1I10CHEMISTRV Freedom to Assoclatc The pr>'Ner-l~enera r. cap ty of n tucho'1drla sbased II redo react OilS (In COmplellES I,ll, III, a d IV) that establish an eleclfo,hem ,at wad e t of pro! '. whle s used to make 1\1 P (In co lple:1 VAR~H:?OO5 ;~.n Itft.. (~ .....lJt1 1377 124 APPENDIX C SUPPLEMENTAL INFORMATION FOR AIl3 SYNTHESIS Figure C.Ol. Crystal-Structure-o£J'T-G51-----­ Table C.Ol. Crystal data and structure refinement for jtg51sx. Identification code jtg51 sx Empirical fOLmula C3 H7 Ga N8 012 Formula weight 416.89 Temperature 153(2) K Wavelength 0.71073 A Crystal system Monoclinic Space group P2(1)/n Unit cell dimensions a =4.2248(11) A a= 900 • b =16.046(4) A b= 96.281(4t. c =8.995(2) A g =900 • Volume 606.1(3) A3 z 1 Density (calculated) 1.142 Mg/m3 Absorption coefficient 1.186 mm-1 125 P(OOO) Crystal size Theta range for data collection Index ranges Reflections collected Independent reflections Completeness to theta = 28.22° Absorption correction Max. and min. transmission Refinement method Data / restraints / parameters Goodness-of-fit on p2 Pinal R indices [1>2sigma(I)] R indices (all data) Largest diff. peak and hole 208 0.20 x 0.10 x 0.10 mm3 2.54 to 28.22°. -5<=h<=5, -20<=k<=21, -11<=1<=11 4938 1404 [R(int) = 0.0313] 93.9 % Semi-empirical from equivalents 1.000 and 0.705 Pull-matrix least-squares on p2 1404/0/114 1.033 Rl = 0.0456, wR2 = 0.1028 Rl =0.0632,wR2=0.1128 0.240 and -0.247 e.A-3 126 Table C.02. Atomic coordinates (x 104) and equivalent isotropic displacement parameters (A2x 103) for jtg51sx. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. x y z U(eq) N(1) 7057(3) 640(1) 1266(2) 23(1) N(2) 9442(3) 967(1) -771(1) 23(1) N(3) 10127(3) 1486(1) -1848(2) 26(1) N(4) 6728(4) 2020(1) 523(2) 30(1) 0(1) 9100(3) 2228(1) -1976(1) 36(1) 0(2) 11837(3) 1203(1) -2763(1) 35(1) C(1) 7272(5) 975(1) 3981(2) 35(1) C(2) 5246(4) 736(1) 2547(2) 26(1) C(3) 7699(4) 1246(1) 334(2) 21(1) Table C.03. Bond lengths [A] and C(1)-H(1C) 0.98(2) angles [0] for jtg51sx. C(2)-H(2A) 0.975(19) C(2)-H(2B) 0.964(18) N(1)-C(3) 1.331(2) N(1)-C(2) 1.459(2) C(3)-N(1)-C(2) 125.45(14) N(1)-H(1) 0.83(2) C:(3)-N(1)-H(1) 114.9(13) N(2)-N(3) 1.3332(18) C:(2)-N(1)-H(1) 119.6(13) N(2)-C(3) 1.375(2) N(3)-N(2)-C:(3) 119.83(13) N(3)-0(2) 1.2392(17) 0(2)-N(3)-0(1) 120.15(13) N(3)-0(1) 1.2685(17) 0(2)-N(3)-N(2) 116.22(13) N(4)-C(3) 1.325(2) 0(1)-N(3)-N(2) 123.62(13) N(4)-H(4A) 0.86(2) C(3)-N(4)-H(4A) 120.3(12) N(4)-H(4B) 0.86(2) C(3)-N(4)-H(4B) 111.1(14) C(1)-C(2) 1.518(3) H(4A)-N(4)-H(4B) 128.1(19) C(1)-H(1A) 0.99(2) C(2)-C(1)-H(1A) 109.6(12) C(1)-H(1B) 0.99(2) C(2)-C(1)-H(1B) 110.9(12) 127 H(IA)-C(1)-H(IB) 109.8(16) C(l)-C(2)-H(2B) 111.1(11) C(2)-C(l)-H(1C) 110.0(12) H(2A)-C(2)-H(2B) 108.0(15) H(IA)-C(I)-H(IC) 109.6(18) N(4)-C(3)-N(1) 121.12(15) H(IB)-C(I)-H(IC) 106.8(16) N(4)-C(3)-N(2) 126.59(14) N(l)-C(2)-C(I) 113.71(15) N(I)-C(3)-N(2) 112.29(13) N(I)-C(2)-H(2A) 106.3(10) C(1)-C(2)-H(2A) 109.7(10) Symmetry transformations used to N(I)-C(2)-H(2B) 107.8(11) generate equivalent atoms: Table C.04. Anisotropic displacement parameters (A2x 103) for jtg51sx. The anisotropic displacement factor exponent takes the form: -2p2[ h2 a*2V11 + ... + 2 h k a* b* V12] V11 V22 V33 V23 V13 V12 N(1) 32(1) 14(1) 25(1) 0(1) 8(1) 1(1) N(2) 33(1) 14(1) 23(1) 1(1) 8(1) 2(1) N(3) 36(1) 16(1) 25(1) 0(1) 7(1) -1(1) N(4) 49(1) 15(1) 29(1) 1(1) 17(1) 4(1) 0(1) 59(1) 15(1) 38(1) 7(1) 20(1) 7(1) 0(2) 51(1) 26(1) 31(1) 0(1) 20(1) 4(1) C(l) 44(1) 37(1) 25(1) 0(1) 5(1) 5(1) C(2) 32(1) 18(1) 29(1) 1(1) 10(1) 0(1) C(3) 27(1) 16(1) 21(1) -1(1) 1(1) 0(1) Table C.OS. Hydrogen coordinates (x 104) and isotropic displacement parameters (A2x 10 3) for jtg51sx. x z V(eq)Y H(I) 7850(40) 182(13) 1100(20) 34(5) H(1A) 8360(50) 1512(14) 3840(20) 45(6) H(lB) 5960(50) 1024(13) 4820(20) 44(6) 128 H(1C) 8860(50) 541(14) 4260(20) 48(6) H(2A) 4220(40) 201(12) 2678(19) 30(5) H(2B) 3600(40) 1144(11) 2290(20) 26(5) H(4A) 5890(50) 2155(11) 1320(20) 32(5) H(4B) 7270(50) 2344(13) -170(20) 40(5) Table C.06. Hydrogen bonds for jtg51sx [A and 0]. D-H...A d(D-H) d(H...A) d(D...A) «DHA) N(1)-H(1)...N(2)#1 0.83(2) 2.21(2) 3.0284(19) 172.4(18) N(4)-H(4A)...O(1)#2 0.86(2) 2.04(2) 2.880(2) 165.5(17) N(4)-H(4B)...O(1) 0.86(2) 1.88(2) 2.581(2) 137.1(19) Symmetry transfonnations used to generate equivalent atoms: #1 -x+2,-y,-z #2 x-l/2,-y+l/2,z+l/2 129 Figure C.02. Crystal structure of Jasonl - Ga(cupferron)3 Table C.07. Crystal data and structure refinement for jason1. Identification code jason1 Empirical formula C18 H15 Gal N6 06 Formula weight 482.58 Temperature 153(2) K Wavelength 0.71073 A Crystal system Monoclinic Space group P2(l)/n Unit cell dimensions a = 11.1379(7) A a= 90°. b = 17.0528(11) A b= 108.2530(lOt. c = 11.1715(7) A g = 90°. Volume 2015.1(2) A3 z 4 Density (calculated) 1.586 Mg/m3 Absorption coefficient 1.415 mrn-1 F(OOO) 976 Crystal size 0.25 x 0.18 x 0.10 mrn3 Theta range for data collection 2.25 to 28.26°. 130 Index ranges -14<=h<=14, -21<=k<=22, -14<=1<=14 Reflections collected 17221 Independent reflections 4710 [R(int) = 0.0289] Completeness to theta = 28.26° 94.4 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 1.000 and 0.835 Refinement method Pull-matrix least-squares on p2 Data / restraints / parameters 4710/0/340 Goodness-of-fit on p2 1.048 Pinal R indices [1>2sigma(l)] Rl = 0.0333, wR2 = 0.0679 R indices (all data) Rl = 0.0486, wR2 = 0.0741 Largest diff. peak and hole 0.316 and -0.291 e.A-3 Table C.OS. Atomic coordinates (x 104) and equivalent isotropic displacement parameters (A2x 103) for jason1. U(eq) is defined as one third of the trace of the orthogonalized uij tensor. x y z U(eq) Ga(l) 4603(1) 7703(1) 10283(1) 24(1) 0(1) 4019(1) 7729(1) 8433(1) 28(1) 0(2) 5889(1) 8391(1) 9965(1) 28(1) 0(3) 5421(1) 6696(1) 10231(1) 28(1) 0(4) 5548(1) 7558(1) 12080(1) 29(1) 0(5) 3751(1) 8639(1) 10646(1) 28(1) 0(6) 2996(1) 7248(1) 10343(1) 32(1) N(l) 4779(2) 8172(1) 8024(2) 25(1) N(2) 5753(2) 8519(1) 8773(2) 28(1) N(3) 6093(2) 6478(1) 11386(2) 22(1) N(4) 6173(2) 6898(1) 12362(2) 26(1) N(5) 2654(2) 8442(1) 10794(2) 24(1) N(6) 2235(2) 7735(1) 10644(2) 30(1) C(1) 4509(2) 8257(1) 6682(2) 27(1) 131 C(2) 3653(2) 7748(1) 5898(2) 32(1) C(3) 3437(2) 7810(2) 4609(2) 40(1) C(4) 4059(3) 8366(2) 4138(2) 48(1) C(5) 4878(3) 8885(2) 4933(2) 46(1) C(6) . 5118(2) 8836(2) 6224(2) 38(1) C(7) 6743(2) 5738(1) 11528(2) 23(1) C(8) 6581(2) 5284(1) 10468(2) 31(1) C(9) 7168(2) 4561(1) 10600(3) 38(1) C(10) 7908(2) 4305(2) 11766(3) 40(1) C(11) 8090(2) 4778(2) 12817(2) 38(1) C(12) 7509(2) 5500(1) 12710(2) 29(1) C(13) 1931(2) 9051(1) 11145(2) 25(1) C(14) 887(2) 8850(2) 11505(2) 39(1) C(15) 212(2) 9446(2) 11830(3) 45(1) C(16) 570(2) 10216(2) 11805(3) 43(1) C(17) 1621(2) 10401(2) 11463(3) 41(1) C(18) 2316(2) 9816(1) 11133(2) 33(1) Table C.09. Bond lengths [A] and O(6)-N(6) 1.305(2) angles [0] for jason1. N(1)-N(2) 1.288(2) N(1)-C(1) 1.441(3) Ga(1)-O(3) 1.9531(14) N(3)-N(4) 1.284(2) Ga(1)-O(1) 1.9633(14) N(3)-C(7) 1.439(2) Ga(1)-O(5) 1.9636(14) N(5)-N(6) 1.285(2) Ga(1)-O(4) 1.9687(15) N(5)-C(13) 1.440(3) Ga(1)-O(2) 1.9694(14) C(1)-C(2) 1.381(3) Ga(1)-O(6) 1.9710(15) C(1)-C(6) 1.384(3) O(1)-N(1) 1.318(2) C(2)-C(3) 1.388(3) O(2)-N(2) 1.309(2) C(2)-H(2) 0.91(2) O(3)-N(3) 1.325(2) C(3)-C(4) 1.372(4) O(4)-N(4) 1.309(2) C(3)-H(3) 0.97(3) O(5)-N(5) 1.327(2) C(4)-C(5) 1.377(4) 132 C(4)-H(4) 0.94(3) ()(1)-Cia(1)-()(2) 79.39(6) C(5)-C(6) 1.384(3) ()(5)-Cia(1)-()(2) 88.77(6) C(5)-H(5) 0.91(3) ()(4)-Cia(1)-()(2) 94.14(6) C(6)-H(6) 0.96(3) ()(3)-Cia(1)-()(6) 95.29(6) C(7)-C(8) 1.378(3) ()(1)-Cia(1)-()(6) 92.27(6) C(7)-C(12) 1.389(3) ()(5)-Cia(1)-()(6) 79.09(6) C(8)-C(9) 1.382(3) ()(4)-Cia(1 )-()(6) 96.74(6) C(8)-H(8) 0.92(2) ()(2)-Cia(1 )-()(6) 163.90(6) C(9)-C(10) 1.376(4) ~(l)-()(l)-Cia(l) 109.96(11) C(9)-H(9) 0.94(3) ~(2)-()(2)-Cia(1) 115.04(12) C(1O)-C(11) 1.387(4) ~(3)-()(3)-Cia(1) 110.15(11) C(10)-H(IO) 0.91(3) ~(4)-()(4)-Cia(1) 115.27(11) C(11)-C(12) 1.379(3) ~(5)-()(5)-Cia(1) 110.07(11) C(l1)-H(11) 0.89(2) ~(6)-()(6)-Cia(1) 115.35(12) C(12)-H(12) 0.92(2) ~(2)-~(1)-()(1) 122.61(16) C(13)-C(18) 1.375(3) ~(2)-~(1)-C(1) 119.25(17) C(13)-C(14) 1.387(3) ()(l)-~(l)-C(l) 118.14(16) C(14)-C(15) 1.379(3) ~(1)-~(2)-()(2) 112.99(16) C(14)-H(14) 0.94(3) ~(4)-~(3)-()(3) 122.51(16) C(15)-C(16) 1.375(4) ~(4)-~(3)-C(7) 119.79(16) C(15)-H(15) 0.90(3) ()(3)-~(3)-C(7) 117.71(15) C(16)-C(17) 1.376(3) ~(3)-~(4)-()(4) 112.67(16) C(16)-H(16) 0.92(3) ~(6)-~(5)-()(5) 122.19(16) C(17)-C(18) 1.382(3) ~(6)-~(5)-C(13) 120.01(17) C(17)-H(17) 0.95(3) ()(5)-~(5)-C(13) 117.80(16) C( 18)-H(18) 0.93(2) ~(5)-~(6)-()(6) 113.12(17) C(2)-C(1 )-C(6) 122.4(2) ()(3)-Cia(1)-()(1) 89.59(6) C(2)-C(1)-~(1) 118.26(19) ()(3)-Cia(1)-()(5) 168.87(6) C(6)-C(1)-~(1) 119.3(2) ()(1)-Cia(1)-()(5) 100.16(6) C(1)-C(2)-C(3) 118.0(2) ()(3)-Cia(1)-()(4) 79.32(6) C(1)-C(2)-H(2) 119.4(15) ()(1)-Cia(1)-()(4) 166.28(6) C(3)-C(2)-H(2) 122.5(15) ()(5)-Cia(1)-()(4) 91.72(6) C(4)-C(3)-C(2) 120.5(2) ()(3)-Cia(1)-()(2) 98.38(6) C(4)-C(3)-H(3) 118.6(15) 133 C(2)-C(3)-H(3) 120.9(16) C(1l)-C(12)-C(7) 118.4(2) C(3)-C(4)-C(5) 120.5(2) C(11)-C(12)-H(12) 122.2(14) C(3)-C(4)-H(4) 120.5(18) C(7)-C(12)-H(12) 119.4(14) C(5)-C(4)-H(4) 119.0(18) C(18)-C(13)-C(14) 121.9(2) C(4)-C(5)-C(6) 120.5(3) C(18)-C(13)-N(5) 118.59(18) C(4)-C(5)-H(5) 123.2(17) C(14)-C(13)-N(5) 119.5(2) C(6)-C(5)-H(5) 116.3(17) C(15)-C(14)-C(13) 118.1(2) C(1)-C(6)-C(5) 118.0(2) C(15)-C(14)-H(14) 123.5(17) C(1)-C(6)-H(6) 119.9(15) C(13)-C(14)-H(14) 118.4(17) C(5)-C(6)-H(6) 122.1(15) C(16)-C(15)-C(14) 120.8(2) C(8)-C(7)-C(12) 121.9(2) C(16)-C(15)-H(15) 120.8(16) C(8)-C(7)-N(3) 118.14(18) C(14)-C(15)-H(15) 118.4(17) C(12)-C(7)-N(3) 119.92(18) C(15)-C(16)-C(17) 120.1(2) C(7)-C(8)-C(9) 118.6(2) C(15)-C(16)-H(16) 120.1(16) C(7)-C(8)-H(8) 118.8(14) C(17)-C(16)-H(16) 119.8(16) C(9)-C(8)-H(8) 122.6(14) C(16)-C(17)-C(18) 120.4(2) C(1O)-C(9)-C(8) 120.5(2) C(16)-C(17)-H(17) 121.5(15) C(1O)-C(9)-H(9) 120.8(16) C(18)-C(17)-H(17) 118.1(15) C(8)-C(9)-H(9) 118.7(16) C(13)-C(18)-C(17) 118.7(2) C(9)-C(1O)-C(11) 120.2(2) C(13)-C(18)-H(18) 120.8(16) C(9)-C(10)-H(10) 120.3(16) C(17)-C(18)-H(18) 120.5(16) C(11)-C(10)-H(10) 119.5(16) C(12)-C(11)-C(l0) 120.4(2) Symmetry transformations used to C(12)-C(11)-H(11) 120.5(17) generate equivalent atoms: C(1O)-C(11)-H(11) 119.1(16) Table C.lO. Anisotropic displacement parameters (A2x 103) for jason1. The anisotropic displacement factor exponent takes the form: -2p2[ h2 a*2U11 + ... + 2 h k a* b* U12] U11 U22 U33 U23 U13 U12 Ga(1) 26(1) 20(1) 25(1) -2(1) 7(1) 2(1) 0(1) 26(1) 28(1) 28(1) 0(1) 7(1) -5(1) 0(2) 28(1) 31(1) 25(1) -4(1) 6(1) -3(1) 134 0(3) 33(1) 25(1) 21(1) -1(1) 3(1) 8(1) 0(4) 36(1) 22(1) 27(1) -3(1) 9(1) 5(1) 0(5) 24(1) 23(1) 37(1) -1(1) 13(1) -1(1) 0(6) 34(1) 20(1) 43(1) -5(1) 16(1) 0(1) N(1) 24(1) 24(1) 27(1) -1(1) 7(1) 2(1) N(2) 28(1) 29(1) 28(1) -3(1) 9(1) -1(1) N(3) 24(1) 20(1) 23(1) 0(1) 6(1) -1(1) N(4) 30(1) 22(1) 26(1) -2(1) 9(1) 1(1) N(5) 24(1) 22(1) 26(1) -1(1) 7(1) 0(1) N(6) 32(1) 23(1) 37(1) -3(1) 13(1) -1(1) C(1) 25(1) 31(1) 25(1) 0(1) 8(1) 10(1) C(2) 29(1) 34(1) 31(1) -4(1) 7(1) 5(1) C(3) 36(1) 50(2) 32(1) -8(1) 4(1) 6(1) C(4) 44(2) 72(2) 25(1) 3(1) 9(1) 14(1) C(5) 43(2) 63(2) 35(1) 12(1) 15(1) -2(1) C(6) 37(1) 44(2) 32(1) 2(1) 11(1) -3(1) C(7) 20(1) 18(1) 32(1) 2(1) 9(1) -2(1) C(8) 28(1) 27(1) 36(1) -3(1) 6(1) 1(1) C(9) 37(1) 26(1) 49(2) -9(1) 11(1) 3(1) C(10) 39(1) 24(1) 61(2) 7(1) 20(1) 8(1) C(11) 38(1) 34(1) 41(1) 17(1) 11(1) 8(1) C(12) 30(1) 27(1) 30(1) 3(1) 10(1) 0(1) C(13) 23(1) 26(1) 25(1) -3(1) 6(1) 4(1) C(14) 31(1) 35(1) 54(2) -3(1) 17(1) -2(1) C(15) 31(1) 49(2) 62(2) -9(1) 24(1) 2(1) C(16) 34(1) 42(2) 54(2) -12(1) 17(1) 9(1) C(17) 41(1) 31(1) 53(2) -7(1) 19(1) 2(1) C(18) 33(1) 27(1) 42(1) -2(1) 17(1) 1(1) 135 Table C.H. Hydrogen coordinates ( x 104) and isotropic displacement parameters (A2x 10 3) for jasonl. x y z U(eq) H(2) 3280(20) 7371(14) 6240(20) 34(7) H(3) 2870(30) 7452(15) 4030(30) 48(8) H(4) 3930(30) 8400(16) 3270(30) 60(8) H(5) 5300(20) 9266(17) 4660(20) 57(9) H(6) 5670(20) 9199(15) 6800(20) 43(7) H(8) 6080(20) 5471(13) 9710(20) 32(6) H(9) 7070(20) 4254(15) 9870(20) 45(7) H(1O) 8260(20) 3819(15) 11860(20) 43(7) H(ll) 8580(20) 4607(15) 13560(20) 43(7) H(12) 7600(20) 5823(13) 13400(20) 28(6) H(14) 690(30) 8314(16) 11540(30) 55(8) H(15) -470(20) 9319(15) 12070(20) 46(7) H(16) 110(20) 10608(15) 12010(20) 46(7) H(17) 1890(20) 10927(15) 11460(20) 42(7) H(18) 3000(20) 9942(14) 10870(20) 45(7) H i3 S H i3 A 3 H i6 A ~i 08 88 38 Fi gu re C .0 3. C ry st al s tr uc tu re o f J TG 27 . . . . . . . w 0 \ 137 Table C.12. Crystal data and structure refinement for jtg27. Identification code jtg27 Empirical formula H88 AlB N15 0101 Pormula weight 2265.59 Temperature 153(2) K Wavelength 0.71073 :::: Crystal system Triclinic Space group P-1 Unit cell dimensions a = 12.8256(8) A a= 77.6010(10)°. b = 13.1667(8) A b= 74.0590(10)°. c = 13.4201(8) A g = 87.6480(10)°. Volume 2127.9(2) ::::3 z 1 Density (calculated) 1.768 Mg/m3 Absorption coefficient 0.311 mm- l P(OOO) 1170 Crystal size 0.31 x 0.18 x 0.09 mm3 Theta range for data collection 1.58 to 28.29°. Index ranges -15<=h<=16, -17<=k<=16, -17<=1<=17 Reflections collected 22455 Independent reflections 9682 [R(int) = 0.0203] Completeness to theta = 28.2900 91.8 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 1.000 and 0.570 Refinement method Pull-matrix least-squares on p2 Data / restraints / parameters 9682 / 26 / 542 Goodness-of-fit on p2 1.069 Pinal R indices [I>2sigma(I)] R1 = 0.0479, wR2 = 0.1264 R indices (all data) R1 = 0.0571, wR2 = 0.1322 Largest diff. peak and hole 0.862 and -0.434 e.::::-3 138 Table C.13. Bond lengths [A] and angles [0] for jtg27. A1(5)-0(8) 1.8581(17) A1(1)-0(2) 1.8710(14) A1(5)-0(7) 1.8722(17) A1(1)-0(2)#1 1.8710(14) A1(5)-0(16) 1.8961(18) A1(1)-0(1) 1.8823(14) A1(5)-0(15) 1.9095(19) A1(1)-0(1)#1 1.8823(14) A1(5)-0(14) 1.9146(18) A1(1)-0(3)#1 1.8850(15) A1(5)-0(13) 1.9306(18) A1(1)-0(3) 1.8850(15) A1(6)-0(9) 1.8492(18) A1(1)-A1(4) 2.9640(6) A1(6)-0( 10) 1.8593(17) A1(1)-A1(4)#1 2.9640(6) A1(6)-0(19) 1.898(2) A1(1)-A1(3)#1 2.9782(6) A1(6)-0(20) 1.9051(19) A1(1)-A1(3) 2.9782(6) A1(6)-0(17) 1.9346(19) A1(2)-0(12)#1 1.8440(17) A1(6)-0( 18) 1.9390(18) A1(2)-0(4) 1.8442(16) A1(7)-0(11) 1.8548(17) A1(2)-0(7) 1.8459(17) A1(7)-0( 12) 1.8676(18) A1(2)-0(6)#1 1.8588(16) A1(7)-0(24) 1.9079(18) A1(2)-0(1) 2.0233(16) A1(7)-0(23) 1.909(2) A1(2)-0(3)#1 2.0328(16) A1(7)-0(22) 1.9165(18) A1(2)-A1(4)#1 2.9843(9) A1(7)-0(21) 1.9389(18) A1(2)-A1(3) 2.9923(9) O(1)-H(1) 0.87(3) A1(3)-0(5) 1.8456(17) 0(2)-H(2) 0.903(19) A1(3)-0(8) 1.8459(17) 0(3)-A1(2)#1 2.0328(16) A1(3)-0(4) 1.8461(16) 0(3)-H(3) 0.74(4) A1(3)-0(9) 1.8472(17) 0(4)-H(4) 0.78(4) A1(3)-0(2) 2.0022(16) 0(5)-H(5) 0.66(4) A1(3)-0(1) 2.0166(16) 0(6)-A1(2)#1 1.8588(16) A1(3)-A1(4) 2.9728(9) 0(6)-H(6) 0.74(4) A1(4)-0(6) 1.8327(17) 0(7)-H(7) 0.71(3) A1(4)-0(5) 1.8407(17) 0(8)-H(8) 0.73(3) A1(4)-O(10) 1.8469(16) 0(9)-H(9) 0.66(3) A1(4)-0(11) 1.8525(16) 0(10)-H(1O) 0.73(4) A1(4)-0(3) 1.9822(16) 0(11)-H(11) 0.78(3) A1(4)-0(2) 2.0051(16) O( 12)-A1(2)#1 1.8440(17) A1(4)-A1(2)#1 2.9843(9) 0(l2)-H(12) 0.66(3) 139 0(13)-H(13A) 0.961(19) O(13)-H(13B) 0.989(19) 0(2)-A1(1)-0(2)#1 180.0 0(14)-H(14A) 1.003(19) 0(2)-A1(1)-0(1) 83.27(6) 0(14)-H(14B) 0.989(19) 0(2)#1-A1(1)-0(l) 96.73(6) 0(15)-H(15A) 0.992(19) 0(2)-Al(1)-0(1)#1 96.73(6) 0(15)-H(15B) 0.972(19) 0(2)#1-Al(1)-0(1)#1 83.27(6) 0(16)-H(16A) 0.954(19) O(l)-Al(l)-O(l)#l 180.0 0(16)-H(16B) 0.961(19) 0(2)-AI(1)-0(3)#1 96.99(6) 0(17)-H(17A) 1.00(2) 0(2)#1-AI(1)-0(3)#1 83.01(6) 0(17)-H(17B) 0.99(2) 0(1)-AI(1)-0(3)#1 83.14(6) 0(17)-H(17C) 0.977(19) 0(1)#I-AI(1)-0(3)#1 96.86(6) 0(18)-H(18A) 0.951(19) 0(2)-AI(I)-0(3) 83.01(6) 0(18)-H(18B) 0.980(19) 0(2)#I-AI(1)-0(3) 96.99(6) 0(19)-H(19A) 0.98(2) 0(1)-AI(I)-0(3) 96.86(6) 0(19)-H(19B) 1.013(19) 0(1)#I-AI(1)-0(3) 83.14(6) 0(20)-H(20A) 0.98(2) 0(3)#1-AI(1)-0(3) 180.0 0(20)-H(20B) 0.926(18) 0(2)-AI(1)-Al(4) 41.82(5) 0(21)-H(21A) 0.965(19) 0(2)#I-AI(1)-AI(4) 138.18(5) 0(21)-H(21B) 0.952(19) 0(l)-AI(1)-AI(4) 89.80(5) 0(22)-H(22A) 0.977(19) 0(1)#I-AI(1)-AI(4) 90.21(5) 0(22)-H(22B) 0.983(19) 0(3)#I-Al(1)-AI(4) 138.81(5) 0(23)-H(23A) 0.98(2) 0(3)-AI(l)-AI(4) 41.19(5) 0(23)-H(23B) 0.983(19) 0(2)-AI(1)-AI(4)#1 138.18(5) 0(24)-H(24A) 0.957(19) 0(2)#I-AI(l)-Al(4)#1 41.82(5) 0(24)-H(24B) 0.964(18) 0(1 )-AI(1)-AI(4)#1 90.20(5) N(1S)-0(3S) 1.235(3) 0(1)#I-AI(1)-AI(4)#1 89.79(5) N(IS)-O(1S) 1.252(3) 0(3)#l-AI(1)-AI(4)#1 41.19(5) N(IS)-0(2S) 1.255(3) 0(3)-AI(1)-AI(4)#1 138.81(5) N(2S)-0(4S) 1.197(3) AI(4)-AI(1)-AI(4)#1 180.0 N(2S)-0(6S) 1.250(3) 0(2)-AI(1)-AI(3)#1 138.62(5) N(2S)-0(5S) 1.256(3) 0(2)#I-Al(1)-AI(3)#1 41.38(5) N(3S)-0(8S) 1.229(3) O(l)-AI( l)-AI(3)#1 138.11(5) N(3S)-0(9S) 1.236(3) 0(1)#I-AI(1)-AI(3)#1 41.89(5) N(3S)-0(7S) 1.244(3) 0(3)#I-AI(1)-AI(3)#1 90.20(5) 140 0(3)-AI(I)-AI(3)#1 89.80(5) 0(4)-AI(2)-AI(3) 35.84(5) AI(4)-AI(I)-AI(3)#1 119.963(17) 0(7)-AI(2)-AI(3) 86.55(6) AI(4)#I-AI(I)-AI(3)#1 60.037(17) 0(6)#I-AI(2)-AI(3) 132.45(6) 0(2)-AI(I)-AI(3) 41.38(5) 0(1)-AI(2)-AI(3) 42.12(4) 0(2)#I-AI(1)-AI(3) 138.62(5) 0(3)#1-Al(2)-AI(3) 86.69(5) 0(1)-AI(I)-AI(3) 41.89(5) AI(4)#I-AI(2)-AI(3) 118.83(3) 0(1)#I-AI(I)-AI(3) 138.11(5) 0(5)-AI(3)-0(8) 97.76(8) 0(3)#I-AI(1)-AI(3) 89.80(5) 0(5)-AI(3)-0(4) 164.18(8) 0(3)-AI(1)-AI(3) 90.20(5) 0(8)-AI(3)-0(4) 90.72(7) AI(4)-AI(1)-AI(3) 60.037(17) 0(5)-AI(3)-0(9) 93.34(8) AI(4)#I-AI(I)-AI(3) 119.964(17) 0(8)-AI(3)-0(9) 102.40(8) AI(3)#I-AI(I)-AI(3) 180.00(2) 0(4)-AI(3)-0(9) 97.87(8) 0(12)#I-AI(2)-0(4) 98.17(8) 0(5)-AI(3)-0(2) 77.62(7) 0(12)#I-AI(2)-0(7) 103.20(8) 0(8)-AI(3)-0(2) 166.88(7) 0(4)-AI(2)-0(7) 91.80(8) 0(4)-AI(3)-0(2) 91.15(7) 0(12)#I-AI(2)-0(6)#1 90.84(8) 0(9)-AI(3)-0(2) 90.21(7) O(4)-AI(2)-0(6)#1 163.36(8) 0(5)-AI(3)-0(1) 89.00(7) 0(7)-AI(2)-0(6)#1 99.76(8) 0(8)-AI(3)-0(1) 91.04(7) 0(12)#I-AI(2)-0(1) 165.14(8) 0(4)-AI(3)-0(1) 77.46(7) 0(4)-Al(2)-0(1) 77.33(7) 0(9)-AI(3)-0(1 ) 165.90(8) 0(7)-AI(2)-0(1) 91.17(7) 0(2)-AI(3)-0(1) 76.71(6) 0(6)#I-AI(2)-0(1) 90.41(7) 0(5)-AI(3)-AI(4) 36.19(5) 0(12)#I-AI(2)-0(3)#1 89.81(7) 0(8)-AI(3)-AI(4) 133.90(6) 0(4)-AI(2)-0(3)#1 89.47(7) 0(4)-AI(3)-AI(4) 133.24(6) 0(7)-Al(2)-0(3)#1 166.59(7) 0(9)-AI(3)-AI(4) 86.65(6) 0(6)#I-AI(2)-0(3)#1 76.53(7) 0(2)-AI(3)-AI(4) 42.15(4) 0(1)-AI(2)-0(3)#1 76.09(6) 0(1)-AI(3)-AI(4) 87.06(5) 0(12)#I-AI(2)-AI(4)#1 85.39(6) 0(5)-AI(3)-AI(I) 81.77(5) O(4)-AI(2)-AI(4)#1 130.80(6) 0(8)-AI(3)-AI(I) 129.46(6) 0(7)-AI(2)-AI(4)#1 135.38(6) 0(4)-AI(3)-AI(I) 82.53(5) 0(6)#1-AI(2)-AI(4)#1 35.76(5) 0(9)-AI(3)-AI(1) 128.13(6) 0(1)-AI(2)-AI(4)#1 87.00(5) 0(2)-AI(3)-AI(1) 38.15(4) 0(3)#I-AI(2)-AI(4)#1 41.34(4) 0(1)-AI(3)-AI(I) 38.55(4) 0(12)#1-AI(2)-AI(3) 133.82(6) AI(4)-AI(3)-AI(1) 59.743(17) 141 0(5)-Al(3)-Al(2) 131.29(6) 0(2)-Al(4)-Al(3) 42.07(4) 0(8)-Al(3)-Al(2) 85.72(6) Al(1)-Al(4)-Al(3) 60.220(17) O(4)-Al(3)-Al(2) 35.80(5) 0(6)-Al(4)-Al(2)#1 36.35(5) 0(9)-Al(3)-Al(2) 133.55(6) 0(5)-Al(4)-Al(2)#1 133.32(6) 0(2)-Al(3)-Al(2) 88.22(5) 0(10)-Al(4)-Al(2)#1 133.52(6) 0(1)-Al(3)-Al(2) 42.30(4) O(1l)-Al(4)-Al(2)#1 86.70(6) Al(4)-Al(3)-Al(2) 120.20(3) 0(3)-Al(4)-Al(2)#1 42.64(5) Al(1)-Al(3)-Al(2) 60.467(17) 0(2)-Al(4)-Al(2)#1 87.90(5) 0(6)-Al(4)-0(5) 165.52(8) Al(1)-Al(4)-Al(2)#1 60.716(17) 0(6)-Al(4)-0(10) 97.29(8) Al(3)-Al(4)-Al(2)#1 120.92(3) 0(5)-Al(4)-0(10) 91.13(7) 0(8)-Al(5)-0(7) 94.69(8) 0(6)-Al(4)-0(11) 91.31(7) 0(8)-Al(5)-0(16) 93.48(8) 0(5)-Al(4)-0(11) 98.60(8) 0(7)-Al(5)-0(16) 94.35(8) 0(1O)-Al(4)-0(11) 101.25(8) 0(8)-Al(5)-0(15) 92.03(8) 0(6)-Al(4)-0(3) 78.40(7) 0(7)-Al(5)-0(15) 92.07(8) 0(5)-Al(4)-0(3) 90.70(7) O(16)-Al(5)-0(15) 171.17(9) O( lO)-Al(4)-0(3) 166.47(8) 0(8)-Al(5)-0(14) 90.09(8) 0(11)-Al(4)-0(3) 91.73(7) 0(7)-Al(5)-0(14) 174.67(8) 0(6)-Al(4)-0(2) 90.53(7) 0(16)-Al(5)-0(14) 87.72(8) 0(5)-Al(4)-0(2) 77.66(7) 0(15)-Al(5)-0(14) 85.38(9) O(lO)-Al(4)-0(2) 90.05(7) 0(8)-Al(5)-0(13) 176.70(8) 0(11)-Al(4)-0(2) 168.22(7) 0(7)-Al(5)-0(13) 88.52(8) 0(3)-Al(4)-0(2) 77.25(6) 0(16)-Al(5)-0(13) 87.00(8) 0(6)-Al(4)-Al(1) 83.29(5) 0(15)-Al(5)-0(13) 87.11(9) 0(5)-Al(4)-Al(1) 82.25(5) 0(14)-Al(5)-0(13) 86.67(8) 0(10)-Al(4)-Al(l) 128.41(6) 0(9)-Al(6)-0(10) 93.71(8) 0(11)-Al(4)-Al(1) 130.34(6) 0(9)-Al(6)-0(19) 93.85(8) 0(3)-Al(4)-Al(1) 38.77(4) 0(1O)-AI(6)-0(19) 92.68(8) 0(2)-AI(4)-Al(1) 38.48(4) 0(9)-Al(6)-0(20) 93.65(8) 0(6)-Al(4)-Al(3) 132.60(6) 0(10)-Al(6)-0(20) 95.49(8) 0(5)-Al(4)-AI(3) 36.31(5) 0(19)-Al(6)-0(20) 168.53(9) 0(1O)-Al(4)-AI(3) 85.04(5) 0(9)-AI(6)-0(17) 91.53(8) 0(11)-AI(4)-AI(3) 134.89(6) 0(1O)-AI(6)-0(17) 174.46(8) 0(3)-Al(4)-Al(3) 88.52(5) 0(19)-Al(6)-0(17) 85.17(9) 142 0(20)-Al(6)-0(17) 85.96(9) Al(1 )-0(3)-Al(2)#1 100.16(7) 0(9)-Al(6)-0(18) 177.69(8) Al(4)-0(3)-Al(2)#1 96.02(7) 0(10)-Al(6)-0(18) 88.58(8) Al(I)-0(3)-1I(3) 119(3) 0(19)-Al(6)-0(18) 85.78(8) Al(4)-0(3)-1I(3) 121(3) 0(20)-Al(6)-0(18) 86.38(8) Al(2)#1-0(3)-1I(3) 116(3) O(17)-Al(6)-0(18) 86.17(8) Al(2)-0(4)-Al(3) 108.35(8) 0(11 )-Al(7)-0(12) 94.33(8) Al(2)-0(4)-1I(4) 126(3) 0(11)-Al(7)-0(24) 92.91(7) Al(3)-0(4)-1I(4) 124(3) O(12)-Al(7)-0(24) 94.74(8) Al(4)-0(5)-Al(3) 107.50(9) 0(11)-Al(7)-0(23) 94.27(8) Al(4)-O(5)-1I(5) 126(3) 0(12)-Al(7)-0(23) 92.47(8) Al(3)-O(5)-1I(5) 126(3) 0(24)-Al(7)-0(23) 169.41(9) Al(4)-0(6)-Al(2)#1 107.89(9) 0(11)-Al(7)-0(22) 177.52(8) Al(4)-0(6)-1I(6) 133(3) 0(12)-Al(7)-0(22) 88.10(8) Al(2)#1-0(6)-1I(6) 118(3) 0(24)-Al(7)-0(22) 86.43(8) Al(2)-0(7)-Al(5) 133.89(10) 0(23)-Al(7)-0(22) 86.07(9) Al(2)-0(7)-II(7) 116(2) 0(11)-Al(7)-0(21) 90.11(8) Al(5)-0(7)-1I(7) 108(2) 0(12)-Al(7)-0(21) 175.18(8) Al(3)-0(8)-Al(5) 135.32(10) 0(24)-Al(7)-0(21) 86.89(8) Al(3)-0(8)-1I(8) 111(2) 0(23)-Al(7)-0(21 ) 85.32(8) Al(5)-0(8)-1I(8) 114(2) 0(22)-Al(7)-0(2l) 87.48(8) Al(3)-0(9)-Al(6) 135.40(10) Al(I)-0(1)-Al(3) 99.56(7) Al(3)-0(9)-1I(9) 109(3) Al(I)-0(1)-Al(2) 100.60(7) Al(6)-0(9)-1I(9) 114(3) Al(3)-0(1)-Al(2) 95.58(7) Al(4)-0(10)-Al(6) 137.19(10) Al(1 )-0(1)-II(1) 123.2(19) Al(4)-0(10)-1I(10) 107(3) Al(3)-0(1)-II(I) 113.2(19) Al(6)-0(1O)-II(10) 116(3) Al(2)-0(1)-II(1) 119.7(19) Al(4)-0(1l)-Al(7) 134.31(10) Al(1)-0(2)-Al(3) 100.46(7) Al(4)-0(11)-II(1l) 113(2) Al(I)-0(2)-Al(4) 99.70(7) Al(7)-0(11)-1I(11) 112(2) Al(3)-0(2)-Al(4) 95.78(7) Al(2)#1-0(12)-Al(7) 135.38(10) Al(I)-0(2)-1I(2) 130(3) Al(2)#1-0(12)-1I(12) 110(3) Al(3)-0(2)-1I(2) 116(3) Al(7)-0(12)-1I(12) 114(3) Al(4)-0(2)-1I(2) 109(3) Al(5)-0(13)-II(13A) 119(3) Al(1)-0(3)-Al(4) 100.04(7) Al(5)-0(13)-II(13B) 118(3) 143 H(13A)-0(13)-H(13B) 111(4) A1(7)-0(2l)-H(2lB) 130(3) A1(5)-0(14)-H(14A) 127(3) H(21A)-0(21)-H(21B) 105(4) A1(5)-0(14)-H(14B) 123(3) A1(7)-0(22)-H(22A) 120(3) H(14A)-0(14)-H(14B) 109(4) A1(7)-0(22)-H(22B) 119(2) A1(5)-0(15)-H(15A) 124(3) H(22A)-0(22)-H(22B) 110(4) A1(5)-0(15)-H(15B) 127(3) A1(7)-0(23)-H(23A) 131(4) H(15A)-0(15)-H(15B) 104(4) A1(7)-0(23)-H(23B) 119(3) A1(5)-0(16)-H(16A) 126(3) H(23A)-0(23)-H(23B) 109(5) A1(5)-0(16)-H(16B) 127(2) A1(7)-0(24)-H(24A) 122(3) H(16A)-0(16)-H(16B) 106(4) A1(7)-0(24)-H(24B) 125(2) A1(6)-0(17)-H( 17A) 107(7) H(24A)-0(24)-H(24B) 113(3) A1(6)-0(17)-H(17B) 117(4) 0(3S)-N(IS)-0(1S) 119.9(2) H(17A)-0(17)-H(17B) 88(7) 0(3S)-N(1S)-0(2S) 121.1(2) A1(6)-0(17)-H(17C) 130(3) 0(1 S)-N(1 S)-0(2S) 119.01(19) H(17A)-0(17)-H(17C) 113(7) O(4S)-N(2S)-0(6S) 119.7(3) H(17B)-0(17)-H(17C) 93(5) 0(4S)-N(2S)-0(5S) 120.7(2) A1(6)-0(18)-H(18A) 121(2) 0(6S)-N(2S)-0(5S) 119.6(2) A1(6)-0(18)-H(18B) 137(3) 0(8S)-N(3S)-0(9S) 121.3(2) H(18A)-0(18)-H(18B) 90(4) 0(8S)-N(3S)-0(7S) 118.4(2) A1(6)-0(19)-H(19A) 128(3) 0(9S)-N(3S)-0(7S) 120.2(2) A1(6)-0(19)-H(19B) 111(3) H(19A)-0(19)-H(19B) 121(4) A1(6)-0(20)-H(20A) 125(5) Symmetry transformations used to A1(6)-0(20)-H(20B) 121(2) generate equivalent atoms: H(20A)-0(20)-H(20B) 106(5) #1 -x+l,-y+l,-z A1(7)-0(21)-H(21A) 121(3) Table C.14. Hydrogen bonds for jtg27 [:::::: and 00]. D-H...A d(D-H) d(H. ..A) d(D...A) «DHA) 0(4)-H(4) 0(4S)#2 0.78(4) 2.03(4) 2.800(3) 174(4) 0(5)-H(5) 0(8S)#3 0.66(4) 2.11(4) 2.767(3) 169(4) 144 O(6)-H(6) O(3S)#4 0.74(4) 2.11(4) 2.838(2) 166(4) 0(7)-H(7) O(2S)#5 0.71(3) 2.12(3) 2.828(2) 177(3) O(8)-H(8) O(9S)#3 0.73(3) 2.14(3) 2.864(3) 175(3) O(9)-H(9) O(6S)#6 0.66(3) 2.08(3) 2.733(3) 172(4) O(1O)-H(1O) O(IS)#3 0.73(4) 2.00(4) 2.728(2) 172(4) 0(11)-H(11) 0(7S) 0.78(3) 2.05(3) 2.794(3) 159(3) 0(12)-H(12) O(5S)#3 0.66(3) 2.26(3) 2.915(3) 176(3) 0(14)-H(14A) 0(10S)#31.003(19) 1.64(2) 2.611(3) 163(4) 0(16)-H(16B) O(6S)#60.961(19) 1.73(2) 2.670(3) 167(4) 0(17)-H(17C) O(5S)#60.977(19) 1.85(3) 2.789(3) 160(5) O(18)-H(18A) O(2S)#30.951(19) 1.849(19) 2.795(3) 173(4) O(20)-H(20B) 0(7S) 0.926(18) 1.74(2) 2.639(3) 165(4) O(24)-H(24B) O(IS)#30.964(18) 1.736(19) 2.691(2) 170(3) Symmetry transformations used to generate equivalent atoms: #1 -x+l,-y+l,-z #2 x,y,z-1 #3 -x+l,-y+l,-z+1 #4 x+l,y,z-1 #5 -x,-y+l,-z+1 #6 -x+l,-y+2,-z+1 . 02 8 . 01 8 15 . . . . J 31 r ~5 8 25 ~2 7 Fi gu re C .0 4 Cr ys ta l s tr uc tu re o f J TG 81 . . . . . . +: 0 V I 146 Table C.tS. Crystal data and structure refinement for JTG81. Identification code jtg81 Empirical formula H96 AlB N17 0106 Formula weight 2381.68 Temperature 173(2) K Wavelength 0.71073 A Crystal system Triclinic Space group P-1 Unit cell dimensions a = 12.623(3) A a= 74.877(4)°. b = 13.251(3) A b= 72.419(4)°. c = 13.597(3) A g = 86.790(4)°. Volume 2092.4(8) A3 Z 1 Density (calculated) 1.890 Mg/m3 Absorption coefficient 0.326mm-1 F(OOO) 1232 Crystal size 0.08 x 0.08 x 0.05 mm3 Theta range for data collection 1.59 to 25.00°. Index ranges -14<=h<=15, -15<=k<=15, -16<=1<=16 Reflections collected 15065 Independent reflections 7308 [R(int) = 0.0700] Completeness to theta = 25.00° 99.1 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9839 and 0.9744 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 7308/0/617 Goodness-of-fit on F2 1.051 Final R indices [1>2sigma(l)] R1 = 0.0836, wR2 = 0.1961 R indices (all data) Rl = 0.1399, wR2 = 0.2315 Largest diff. peak and hole 0.811 and -0.588 e.k3 147 Table C.16. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (A2x 103) for JTG81. U(eq) is defined as one third of the trace of the orthogonalized uij tensor. x Al(1) 0 Al(2) 1286(2) Al(3) -340(2) Al(4) -1666(2) Al(5) 2004(2) Al(6) -2958(2) Al(7) -1920(2) 0(1) 860(4) 0(2) -1188(4) 0(3) -344(4) 0(4) 13(4) 0(5) -666(4) 0(6) -2356(4) 0(7) 2180(4) 0(8) 706(4) 0(9) 3370(4) 0(10) 1936(4) 0(11) 1246(4) 0(12) 2955(4) 0(13) -1596(4) 0(14) -2852(4) 0(15) -3246(4) 0(16) -4396(4) 0(17) -2333(4) 0(18) -3687(4) 0(19) -1731(4) 0(20) -1451(4) 0(21) -2384(4) y 0 -210(2) 1484(2) 1698(2) 2127(2) 2365(2) 2692(2) 842(3) 543(3) 1065(3) 330(4) 2382(3) 724(3) 780(4) 2345(4) 2043(4) 3529(4) 1694(4) 2707(4) 1838(3) 1968(4) 2812(4) 2921(4) 3731(4) 1081(4) 2728(4) 1333(4) 4128(4) z U(eq) 0 12(1) 1544(2) 13(1) 1362(2) 12(1) -155(2) 12(1) 1835(2) 15(1) 2176(2) 14(1) -2655(2) 15(1) 394(4) 14(1) 910(4) 10(1) -1077(4) 12(1) 2306(4) 14(1) 207(4) 13(1) -530(4) 13(1) 1662(4) 14(1) 1448(4) 17(1) 2216(4) 21(1) 2026(4) 21(1) 3318(4) 21(1) 405(4) 22(1) 2306(4) 13(1) 925(4) 15(1) 3462(4) 20(1) 2099(4) 18(1) 1443(4) 19(1) 3085(4) 23(1) -1352(4) 15(1) -2624(4) 16(1) -2830(4) 23(1) 148 0(22) -2093(4) 2806(4) -4060(4) 25(1) 0(23) -3437(4) 2301(4) -2083(4) 21(1) 0(24) -444(4) 3242(4) -3423(4) 20(1) N(l) 12198(6) 2897(5) -1806(5) 29(2) 0(25) 12806(5) 3686(5) -2143(5) 44(2) 0(26) 11394(5) 2815(5) -2135(5) 40(2) 0(27) 12418(5) 2124(4) -1097(4) 25(1) N(2) 9740(7) 5986(6) -4097(6) 32(2) 0(28) 8770(5) 5858(5) -4113(5) 45(2) 0(29) 10346(5) 5229(4) -3936(5) 42(2) 0(30) 10121(5) 6897(4) -4260(5) 42(2) N(3) 9982(5) 5076(5) 1233(5) 21(2) 0(31) 10906(5) 5298(4) 1308(5) 37(2) 0(32) 9474(5) 5738(4) 732(4) 28(1) 0(33) 9601(4) 4163(4) 1686(4) 23(1) N(4) 11390(6) -518(5) 5114(5) 26(2) 0(34) 11350(7) -319(5) 4180(5) 53(2) 0(35) 11337(7) 200(5) 5547(5) 52(2) 0(36) 11507(6) -1429(4) 5588(5) 39(2) N(5) 3597(7) 3213(7) 4292(6) 38(2) 0(37) 3249(6) 3395(6) 5196(5) 51(2) 0(38) 3249(5) 2420(5) 4135(5) 44(2) 0(39) 4332(6) 3813(5) 3573(5) 48(2) N(6) 6193(6) 4692(5) -391(6) 29(2) 0(40) 6591(5) 5110(5) 171(5) 39(2) 0(41) 6298(5) 5151(5) -1347(5) 41(2) 0(42) 5673(5) 3840(5) 9(5) 37(2) N(7) 4970(6) 115(5) 1242(5) 21(2) 0(43) 5728(5) -406(4) 837(5) 32(1) 0(44) 4022(4) -302(4) 1756(5) 27(1) 0(45) 5111(4) 1083(4) 1154(5) 29(1) N(8) 5180(7) 2155(7) 6040(6) 40(2) 0(46) 4494(6) 1926(6) 6918(5) 53(2) 0(47) 5281(8) 1633(6) 5392(6) 75(3) 149 0(48) 5792(6) 2956(6) 5761(6) 61(2) O(1S) 11338(5) 2069(4) -3875(5) 35(2) 0(2S) 12613(5) 664(4) -2714(4) 28(1) 0(3S) 14973(6) -3726(6) 2028(7) 71(3) 0(4S) 4217(5) 488(5) 3997(6) 49(2) 0(5S) 12550(5) 5433(4) -3695(5) 37(2) N(IS) 15000 -5000 5000 71(4) Table C.l7. Bond lengths [A] and Al(3)-0(1) 1.996(5) angles [0] for JTG81. Al(3)-0(2) 2.006(5) Al(3)-AI(4) 2.977(3) Al(I)-O(l) 1.873(5) Al(4)-0(5) 1.842(5) Al(l)-O(1)#1 1.873(5) Al(4)-0(14) 1.848(5) Al(I)-0(2) 1.876(5) Al(4)-0(6) 1.850(5) Al(I)-0(2)#1 1.876(5) Al(4)-0(19) 1.852(5) Al(1)-0(3)#1 1.887(5) Al(4)-0(2) 2.018(5) Al(I)-0(3) 1.887(5) Al(4)-0(3) 2.046(5) Al(I)-AI(3) 2.967(2) Al(4)-AI(2)#1 2.995(3) Al(1)-AI(3)#1 2.967(2) Al(5)-0(8) 1.853(5) Al(I)-AI(2) 2.970(2) Al(5)-0(7) 1.853(5) Al(I)-Al(2)#1 2.970(2) Al(5)-0(11) 1.899(5) Al(2)-0(7) 1.846(5) Al(5)-0(12) 1.930(6) Al(2)-0(4) 1.851(5) Al(5)-0(9) 1.935(5) Al(2)-0(20)#1 1.851(5) Al(5)-0(1O) 1.936(5) Al(2)-0(6)#1 1.858(5) Al(6)-0(13) 1.859(5) Al(2)-0(1) 1.991(5) Al(6)-0(14) 1.873(5) Al(2)-0(3)#1 2.020(5) Al(6)-0(17) 1.907(5) Al(2)-AI(3) 2.969(3) Al(6)-0(18) 1.913(5) Al(2)-AI(4)#1 2.995(3) Al(6)-0(15) 1.916(5) Al(3)-0(13) 1.840(5) Al(6)-0(16) 1.943(5) Al(3)-0(8) 1.841(5) Al(7)-0(20) 1.857(5) Al(3)-0(5) 1.847(5) Al(7)-0(19) 1.870(5) Al(3)-0(4) 1.852(5) Al(7)-0(23) 1.881(5) 150 Al(7)-0(24) 1.917(5) 0(1)-Al(l)-0(2)#1 96.72(19) Al(7)-0(2l) 1.935(5) 0(1)#I-Al(1)-0(2)#1 83.28(19) Al(7)-0(22) 1.955(6) 0(2)-Al(1)-0(2)#1 180.0(4) 0(3)-Al(2)#1 2.020(5) 0(l)-Al(1)-0(3)#1 83.47(19) 0(6)-Al(2)#1 1.858(5) 0(1)#l-Al(1)-O(3)#1 96.53(19) 0(20)-Al(2)#1 1.851(5) 0(2)-Al(I)-0(3)#1 96.49(19) N(1)-0(25) 1.233(8) 0(2)#I-Al(I)-0(3)#1 83.51(19) N(1)-0(26) 1.246(9) 0(1)-Al(I)-0(3) 96.53(19) N(I)-0(27) 1.292(8) 0(1)#I-Al(l)-0(3) 83.47(19) N(2)-0(29) 1.241(9) 0(2)-Al(1)-0(3) 83.51(19) N(2)-0(28) 1.253(9) 0(2)#l-Al(1)-0(3) 96.49(19) N(2)-0(30) 1.264(8) 0(3)#I-Al(l)-0(3) 180.0(4) N(3)-0(32) 1.238(8) 0(1)-Al(I)-Al(3) 41.49(15) N(3)-0(33) 1.254(7) 0(1)#l-Al(1 )-Al(3) 138.51(15) N(3)-0(3l) 1.259(8) 0(2)-Al(I)-Al(3) 41.80(14) N(4)-0(35) 1.232(8) 0(2)#I-Al(I)-Al(3) 138.20(14) N(4)-0(36) 1.235(8) 0(3)#l-Al(1)-Al(3) 90.45(14) N(4)-0(34) 1.244(8) 0(3)-Al(l)-Al(3) 89.55(14) N(5)-0(38) 1.252(9) 0(1)-Al(1)-Al(3)#1 138.51(15) N(5)-0(39) 1.256(10) 0(l)#I-Al(1)-Al(3)#1 41.49(15) N(5)-0(37) 1.257(9) 0(2)-Al(1)-Al(3)#1 138.20(14) N(6)-0(42) 1.244(8) 0(2)#l-Al(l)-Al(3)#1 41.80(14) N(6)-0(41) 1.253(9) 0(3)#I-Al(1)-Al(3)#1 89.55(14) N(6)-0(40) 1.275(9) 0(3)-Al(1)-Al(3)#1 90.45(14) N(7)-0(43) 1.226(8) Al(3)-Al( l)-Al(3)#1 180.00(6) N(7)-0(44) 1.262(8) 0(1)-Al(I)-Al(2) 41.25(14) N(7)-0(45) 1.274(8) 0(1)#l-Al( l)-Al(2) 138.75(14) N(8)-0(46) 1.217(9) 0(2)-Al(1)-Al(2) 89.89(14) N(8)-0(47) 1.229(10) 0(2)#l-Al(1)-Al(2) 90.11(14) N(8)-0(48) 1.254(10) 0(3)#l-Al(l)-Al(2) 42.21(14) 0(3)-Al(1)-Al(2) 137.79(14) O(1)-Al(I)-O(I)#1 180.0(3) Al(3)-Al(I)-Al(2) 60.00(6) 0(l)-Al(I)-0(2) 83.28(19) Al(3)#l-Al(1 )-Al(2) 120.00(6) 0(1)#I-Al(I)-0(2) 96.72(19) 0(l)-Al(1)-Al(2)#1 138.75(14) 151 0(1)#1-A1(1)-Al(2)#1 41.25(14) 0(3)#1-A1(2)-Al(1) 38.88(14) 0(2)-Al(1)-Al(2)#1 90.11(14) Al(3)-Al(2)-Al(1) 59.94(6) 0(2)#1-Al(1)-Al(2)#1 89.89(14) 0(7)-Al(2)-Al(4)#1 133.26(18) 0(3)#1-Al(1)-Al(2)#1 137.79(14) 0(4)-Al(2)-Al(4)#1 132.76(18) 0(3)-Al(1)-Al(2)#1 42.21(14) 0(20)#1-Al(2)-Al(4)#1 87.22(17) Al(3)-Al(1)-Al(2)#1 120.00(6) 0(6)#1-Al(2)-Al(4)#1 36.02(15) Al(3)#1-Al(1 )-Al(2)#1 60.00(6) 0(1 )-Al(2)-Al(4)#1 87.69(15) Al(2)-Al(1 )-Al(2)#1 180.00(6) 0(3)#1-Al(2)-Al(4)#1 42.90(14) 0(7)-Al(2)-0(4) 92.0(2) Al(3)-Al(2)-Al(4)#1 120.39(9) 0(7)-Al(2)-0(20)#1 100.3(2) Al(1 )-Al(2)-Al(4)#1 60.45(6) 0(4)-Al(2)-0(20)#1 98.6(2) 0(13)-Al(3)-0(8) 100.5(2) 0(7)-Al(2)-0(6)#1 97.4(2) 0(13)-Al(3)-0(5) 92.0(2) 0(4)-Al(2)-0(6)#1 165.1(2) 0(8)-Al(3)-0(5) 96.4(2) 0(20)#1-Al(2)-0(6)#1 91.1(2) 0(13)-Al(3)-0(4) 97.2(2) 0(7)-Al(2)-0(1) 90.3(2) 0(8)-Al(3)-0(4) 93.8(2) 0(4)-Al(2)-0(1) 77.9(2) 0(5)-Al(3)-0(4) 164.8(2) 0(20)#1-Al(2)-0(1) 169.1(2) 0(13)-Al(3)-0(1) 168.9(2) 0(6)#1-Al(2)-0(1) 90.5(2) 0(8)-Al(3)-0(1) 89.7(2) 0(7)-Al(2)-0(3)#1 166.7(2) 0(5)-Al(3)-0(l) 91.0(2) O(4)-Al(2)-0(3)#1 89.9(2) 0(4)-Al(3)-0(1) 77.8(2) 0(20)#1-Al(2)-0(3)#1 92.5(2) O(13)-Al(3)-0(2) 93.3(2) 0(6)#1-Al(2)-0(3)#1 78.4(2) 0(8)-Al(3)-0(2) 165.3(2) 0(1)-Al(2)-0(3)#1 77.2(2) 0(5)-Al(3)-0(2) 77.8(2) 0(7)-Al(2)-Al(3) 85.77(16) 0(4)-Al(3)-0(2) 89.6(2) 0(4)-Al(2)-Al(3) 36.70(15) 0(1)-Al(3)-0(2) 77.0(2) 0(20)#1-Al(2)-Al(3) 135.27(18) 0(13)-Al(3)-Al(1) 131.67(17) O(6)#1-Al(2)-Al(3) 132.43(17) 0(8)-Al(3)-Al(1) 127.78(18) 0(1)-Al(2)-Al(3) 41.94(15) 0(5)-Al(3)-Al(1) 82.46(15) 0(3)#1-Al(2)-Al(3) 87.89(15) 0(4)-Al(3)-Al(1) 82.38(16) 0(7)-Al(2)-Al(1) 128.44(17) 0(1 )-Al(3)-Al(1) 38.43(14) 0(4)-Al(2)-Al(1) 82.30(16) 0(2)-Al(3)-Al(1) 38.56(13) 0(20)#1-Al(2)-Al(1) 131.29(18) 0(13)-Al(3)-Al(2) 133.83(17) 0(6)#1-Al(2)-Al(1) 82.85(16) 0(8)-Al(3)-Al(2) 86.66(17) 0(1)-Al(2)-Al(1) 38.33(14) 0(5)-Al(3)-Al(2) 132.80(18) 152 0(4)-Al(3)-Al(2) 36.68(15) 0(14)-Al(4)-Al(2)#1 134.63(18) O(1)-Al(3)-Al(2) 41.82(14) 0(6)-Al(4)-Al(2)#1 36.20(15) 0(2)-Al(3)-Al(2) 87.51(15) 0(19)-Al(4)-Al(2)#1 86.25(17) Al(1 )-Al(3)-Al(2) 60.05(6) 0(2)-Al(4)-Al(2)#1 86.77(15) 0(13)-Al(3)-Al(4) 87.38(17) 0(3)-Al(4)-Al(2)#1 42.22(14) 0(8)-Al(3)-Al(4) 132.45(18) Al(3)-Al(4)-Al(2)#1 118.84(9) 0(5)-Al(3)-Al(4) 36.15(15) 0(8)-Al(5)-0(7) 94.7(2) 0(4)-Al(3)-Al(4) 131.99(18) 0(8)-Al(5)-0(11) 93.9(2) 0(1)-Al(3)-Al(4) 88.80(16) 0(7)-Al(5)-0(11) 94.4(2) 0(2)-Al(3)-Al(4) 42.44(14) 0(8)-Al(5)-0(12) 94.1(2) Al(l )-Al(3)-Al(4) 60.70(6) 0(7)-Al(5)-0(12) 91.9(2) Al(2)-Al(3)-Al(4) 120.75(9) 0(1l)-Al(5)-0(12) 169.4(3) 0(5)-Al(4)-0(14) 92.7(2) 0(8)-Al(5)-0(9) 174.6(2) 0(5)-Al(4)-0(6) 163.5(2) 0(7)-Al(5)-0(9) 90.5(2) 0(14)-Al(4)-0(6) 98.6(2) 0(11)-Al(5)-0(9) 87.3(2) 0(5)-Al(4)-0(19) 97.0(2) 0(12)-Al(5)-0(9) 84.2(2) 0(14)-Al(4)-0(19) 103.9(2) 0(8)-Al(5)-0(1O) 89.7(2) 0(6)-Al(4)-0(19) 91.9(2) 0(7)-Al(5)-0(10) 175.5(2) 0(5)-Al(4)-0(2) 77.6(2) 0(1l)-Al(5)-0(1O) 86.0(2) 0(14)-Al(4)-0(2) 90.3(2) 0(12)-Al(5)-0(10) 87.0(2) 0(6)-Al(4)-0(2) 90.2(2) 0(9)-Al(5)-0(1O) 85.0(2) 0(19)-Al(4)-0(2) 165.0(2) 0(13)-Al(6)-0(14) 95.8(2) 0(5)-Al(4)-0(3) 88.2(2) 0(13)-Al(6)-0(17) 92.4(2) 0(14)-Al(4)-0(3) 165.9(2) 0(14)-Al(6)-0(17) 94.4(2) 0(6)-Al(4)-0(3) 77.9(2) 0(13)-Al(6)-0(18) 90.2(2) 0(19)-Al(4)-0(3) 89.9(2) 0(14)-Al(6)-0(18) 93.3(2) 0(2)-Al(4)-0(3) 76.13(19) 0(17)-Al(6)-0(18) 171.6(2) 0(5)-Al(4)-Al(3) 36.27(15) 0(13)-Al(6)-0(15) 91.0(2) 0(14)-Al(4)-Al(3) 86.10(17) 0(14)-Al(6)-0(15) 173.2(2) 0(6)-Al(4)-Al(3) 132.30(17) 0(17)-Al(6)-0(15) 86.4(2) 0(19)-Al(4)-Al(3) 133.17(18) 0(18)-Al(6)-0(15) 85.6(2) 0(2)-Al(4)-Al(3) 42.13(13) 0(13)-Al(6)-0(16) 177.7(2) 0(3)-Al(4)-Al(3) 86.36(15) 0(14)-Al(6)-0(16) 86.5(2) 0(5)-Al(4)-Al(2)#1 130.41(17) 0(17)-Al(6)-0(16) 87.9(2) 153 0(18)-Al(6)-0(16) 89.1(2) Al(4)-0(14)-Al(6) 133.3(3) 0(15)-Al(6)-0(16) 86.8(2) Al(4)-0(19)-Al(7) 133.2(3) 0(20)-Al(7)-0(19) 96.7(2) Al(2)#1-0(20)-Al(7) 133.2(3) 0(20)-Al(7)-0(23) 94.1(2) 0(25)-N(1)-0(26) 122.5(7) 0(19)-Al(7)-0(23) 95.1(2) 0(25)-N(1)-0(27) 118.3(7) 0(20)-Al(7)-0(24) 91.3(2) 0(26)-N(1)-0(27) 119.2(7) O(19)-Al(7)-0(24) 91.7(2) 0(29)-N(2)-0(28) 120.9(7) 0(23)-Al(7)-O(24) 170.7(2) 0(29)-N(2)-0(30) 118.9(8) 0(20)-Al(7)-0(2l) 174.6(2) 0(28)-N(2)-0(30) 120.2(8) 0(19)-Al(7)-0(21) 88.4(2) 0(32)-N(3)-0(33) 121.8(6) 0(23)-Al(7)-0(21) 87.1(2) 0(32)-N(3)-0(31) 121.0(6) 0(24)-Al(7)-0(21) 86.8(2) 0(33)-N(3)-0(31) 117.3(6) 0(20)-Al(7)-0(22) 88.4(2) 0(35)-N(4)-0(36) 120.8(7) 0(19)-Al(7)-0(22) 174.2(2) 0(35)-N(4)-0(34) 119.5(7) 0(23)-Al(7)-0(22) 87.1(2) 0(36)-N(4)-0(34) 119.7(7) 0(24)-Al(7)-0(22) 85.5(2) 0(38)-N(5)-0(39) 121.2(8) 0(21)-Al(7)-0(22) 86.4(2) 0(38)-N(5)-0(37) 120.1(8) Al(1 )-0(1 )-Al(2) 100.4(2) 0(39)-N(5)-0(37) 118.6(8) Al(1 )-0(1)-Al(3) 100.1(2) 0(42)-N(6)-0(41) 119.2(7) Al(2)-0(1)-Al(3) 96.2(2) 0(42)-N(6)-0(40) 120.6(7) Al(1)-0(2)-Al(3) 99.6(2) 0(41)-N(6)-0(40) 120.1(7) Al(1)-0(2)-Al(4) 100.9(2) 0(43)-N(7)-0(44) 120.2(6) Al(3)-0(2)-Al(4) 95.4(2) 0(43)-N(7)-0(45) 121.4(6) Al(l )-0(3)-Al(2)#1 98.9(2) 0(44)-N(7)-0(45) 118.4(6) Al(l)-0(3)-Al(4) 99.5(2) 0(46)-N(8)-0(47) 121.8(9) Al(2)#1-0(3)-Al(4) 94.9(2) 0(46)-N(8)-0(48) 120.3(8) Al(2)-0(4)-Al(3) 106.6(3) 0(47)-N(8)-0(48) 117.8(8) Al(4)-0(5)-Al(3) 107.6(2) Al(4)-O(6)-Al(2)#1 107.8(2) Symmetry transformations used to Al(2)-0(7)-Al(5) 135.7(3) generate equivalent atoms: Al(3)-0(8)-Al(5) 134.6(3) #1 -x,-y,-z Al(3)-0(13)-Al(6) 133.4(3) 154 Table C.tS. Anisotropic displacement parameters (A2x 103)for JTG81. The anisotropic displacement factor exponent takes the form: _2p2[ h2a*2U 11 + ... + 2 h k a* b* U12 ] U11 U22 U33 U23 U13 U12 Al(I) 13(2) 8(2) 16(2) -2(1) -7(1) 2(1) Al(2) 14(1) 9(1) 16(1) -3(1) -7(1) 3(1) Al(3) 12(1) 7(1) 16(1) -3(1) -7(1) 4(1) Al(4) 14(1) 7(1) 15(1) -3(1) -7(1) 5(1) Al(5) 17(1) 9(1) 23(1) -6(1) -10(1) 6(1) Al(6) 14(1) 10(1) 18(1) -4(1) -5(1) 3(1) Al(7) 15(1) 11(1) 19(1) -2(1) -9(1) 5(1) 0(1) 15(3) 6(2) 23(3) -4(2) -10(2) 7(2) 0(2) 10(2) 5(2) 16(3) -1(2) -7(2) 1(2) 0(3) 11(3) 8(2) 19(3) -5(2) -5(2) 2(2) 0(4) 15(3) 12(3) 19(3) -7(2) -9(2) 9(2) 0(5) 18(3) 8(2) 14(3) -1(2) -8(2) 5(2) 0(6) 16(3) 10(2) 14(3) -2(2) -8(2) 1(2) 0(7) 16(3) 10(3) 19(3) -7(2) -8(2) 3(2) 0(8) 18(3) 11(3) 22(3) -5(2) -8(2) 3(2) 0(9) 16(3) 24(3) 28(3) -10(2) -11(2) 6(2) 0(10) 23(3) 16(3) 31(3) -11(2) -13(3) 5(2) 0(11) 23(3) 21(3) 21(3) -7(2) -9(2) 10(2) 0(12) 23(3) 16(3) 23(3) 0(2) -8(2) 2(2) 0(13) 15(3) 7(2) 16(3) -4(2) -3(2) 2(2) 0(14) 15(3) 11(3) 19(3) -3(2) -5(2) 8(2) 0(15) 23(3) 16(3) 19(3) -8(2) -3(2) 4(2) 0(16) 14(3) 17(3) 23(3) -6(2) -5(2) 5(2) 0(17) 19(3) 12(3) 26(3) -4(2) -8(2) 3(2) 0(18) 27(3) 16(3) 23(3) -2(2) -7(2) 4(2) 0(19) 16(3) 12(3) 14(3) 1(2) -6(2) 6(2) 0(20) 17(3) 12(3) 17(3) 1(2) -7(2) 3(2) 0(21) 27(3) 16(3) 29(3) -5(2) -12(3) 8(2) 0(22) 31(3) 22(3) 26(3) -4(2) -17(3) 7(2) 155 0(23) 14(3) 23(3) 25(3) -5(2) -8(2) 4(2) 0(24) 20(3) 12(3) 26(3) -4(2) -4(2) 2(2) N(I) 31(4) 23(4) 30(4) -8(3) -5(3) 1(3) 0(25) 31(4) 29(4) 64(5) 0(3) -12(3) -4(3) 0(26) 39(4) 39(4) 51(4) -15(3) -27(3) 7(3) 0(27) 34(3) 18(3) 17(3) 7(2) -7(3) -8(2) N(2) 40(5) 24(4) 29(4) -10(3) -2(4) 1(4) 0(28) 37(4) 31(4) 61(5) -11(3) -9(3) 5(3) 0(29) 50(4) 18(3) 65(5) -11(3) -28(4) 10(3) 0(30) 54(4) 17(3) 42(4) -15(3) 12(3) -11(3) N(3) 18(4) 15(4) 30(4) -6(3) -7(3) -2(3) 0(31) 28(3) 22(3) 64(4) -5(3) -26(3) 2(3) 0(32) 32(3) 15(3) 35(3) 2(3) -18(3) 7(2) 0(33) 24(3) 6(3) 34(3) 0(2) -6(3) -3(2) N(4) 40(4) 16(4) 21(4) -6(3) -8(3) 6(3) 0(34) 120(7) 25(4) 24(4) -9(3) -36(4) 20(4) 0(35) 111(6) 17(3) 19(3) -7(3) -4(4) -5(4) 0(36) 74(5) 20(3) 29(3) -6(3) -23(3) 14(3) N(5) 38(5) 47(5) 37(5) -25(4) -12(4) 15(4) 0(37) 51(4) 58(5) 45(4) -28(4) -4(4) -3(4) 0(38) 51(4) 42(4) 55(4) -32(4) -25(4) 12(3) 0(39) 48(4) 43(4) 39(4) -10(3) 8(4) 2(3) N(6) 24(4) 25(4) 34(4) 0(3) -11(3) 7(3) 0(40) 44(4) 30(4) 52(4) -5(3) -34(3) 1(3) 0(41) 42(4) 45(4) 32(4) -1(3) -14(3) 4(3) 0(42) 47(4) 21(3) 46(4) -5(3) -22(3) 2(3) N(7) 29(4) 12(3) 23(4) -1(3) -12(3) 3(3) 0(43) 23(3) 22(3) 44(4) -7(3) -1(3) 9(3) 0(44) 17(3) 18(3) 42(4) -5(3) -5(3) -4(2) 0(45) 17(3) 24(3) 50(4) -18(3) -8(3) 3(2) N(8) 48(5) 41(5) 28(5) -1(4) -13(4) -5(4) 0(46) 39(4) 85(6) 28(4) -4(4) -5(3) -18(4) 0(47) 126(8) 42(5) 50(5) -20(4) -12(5) 13(5) 0(48) 57(5) 66(5) 57(5) 8(4) -31(4) -14(4) 156 O(lS) 30(3) 24(3) 51(4) -10(3) -13(3) 11(3) O(2S) 32(3) 16(3) 31(3) -3(2) -6(3) 5(2) O(3S) 34(4) 45(5) 136(8) -42(5) -16(5) 19(3) O(4S) 33(4) 48(4) 61(5) -6(4) -12(3) -3(3) O(5S) 54(4) 21(3) 41(4) -10(3) -19(3) -2(3) N(lS) 49(8) 58(9) 99(11) -42(8) 7(8) 6(7) 10000.0 9000.0 8000.0 7000.0 6000.0 ?' c E5000.0 4000.0 3000.0 2000.0 1000.0 '" 0.0 10.0 I I I 5.0 30.0 35.0 40.0 2 theta Figure C.OS. X-ray powder diffraction pattern calculated from the single crystal structure of1. 157 500 450 400 350 300 t> ] 250 .5 200 150 100 50 0 5 10 15 20 25 30 35 2 theta Figure C.06. X-ray powder diffraction pattern of JTG27. 10000.0 9000.0 8000.0 7000.0 6000.0 ~ ;;; c: ~5000.0 4000.0 3000.0 2000.0 40 45 50 2 theta Figure C.07. X-ray powder diffraction pattern calculated from the single crystal structure ofJTG81. 158 3000 2500 2000 Bj J500 1000 500 o .....JL 1 I I... I j 11 II ~ 1, .I. jL~A ,. ~ 1L.l lL j - . 5 10 15 20 25 30 35 40 45 50 21hela Figure C.08. X-ray powder diffraction pattern ofJTG81. TGA were run at 2°c/min from room temperature up to 600°C then held iosthermic for 5min. 159 Sample: JTG_IL021 File: C: ...IJTG_II_021 Size: 15.8600 mg TGA Operator: TLA Method: JTG Run Date: 11-00t-07 09:44 120 100 80 ~ ~ E 60 '" ~ 40 20 o \ 13.54% (2. 147mg) 50.51% (8.011mg) 17.62% (2.794mg) 1.043% (0.1655mg) ~ o 100 200 300 400 500 600 Universal V2.6D TA Instruments Temperature eel Figure C.09. TGA thennogram of JTG27. 160 Sample: JTG_II_025 File: C:...IJTG II 025 Size: 23.2330 mg TGA Operator. TLA- ­ Method:JTG Run Date: 11·0ct-D7 13:51 120 100 80 >R e.... .E 60 Cl ~ 40 20 ~ 12.82% (2.978mg) 52.53% (12.2Dmg) '~ 17.50% (4.066mg) 0.7561% (0.1757mg) o o 100 200 300 400 500 600 Temperature (oG) UnivElt'6s1 V2.6D TA Instruments Figure C.lO. TGA thermogram of JTG81. 161 APPENDIXD SUPPLEMENTAL INFORMATION FOR HETEROMETALLIC NANOCLUSTERS Other heterometallic clusters GagInSO Ga7In6°Ga9In4° e =Gallium e =Aluminum = Indium Figure D.Ol. Ball and stick representation of crystal structures. EXPERIMETNAL N-nitroso-di-n-butylamine (0.64 g, 4.02 nunol, 24 eq.) is added to a solution of aLuminum(lII) nitrate (0.25 g, 1.2 nunol, 7 eq.) and indium(lII) nitrate (0.30 g, 1.01 mmol, 6 eq.) in 5 rnL of 0.26M NaOH/MeOH. The mixture is allowed to evaporate over 2-5 days at which point crystals begin to form in the same maMer as before. This method 162 affords the AlsIns cluster in 10% yield with respect to aluminum. [Ga7Ga3In3(J.l3-0H)6(J.l-OH)lS(H20)24](N03)lS (Galo1n3) Gallium (III) nitrate (0.5 g, 1.95 mmol, 7 equivalent) and indium (III) nitrate (0.5 g, 1.66 mmol, 6 equivalents) are dissolved in 5mL of methanol and nitrosobenzene (0.7 g, 6.53 mmol, 24 equivalents) is dissolved in 2mL of methanol, the solutions are mixed together. The mixture is allowed to slowly evaporate at room temperature over 4-8 days, yielding large single crystals in 35% yield with respect to gallium nitrate. Alternative reductant. N-nitroso-di-n-butylamine (1.06 g, 6.69 mmol, 24 eq.) is added to Ga(N03)3 (0.5 g, 1.95 mmol, 7 eq.) and In(N03)3 (0.5 g,' 1.66 mmol, 6 eq.) in methanol, as a homogenous solution. The mixture is allowed to evaporate over 2-5 days at which point crystals begin to form in the same manner as before. This alternative method produces the same Ga7In6 cluster in 47% yield with respect to gallium. More crystals can be isolated by ppt from the oil with EtOAc, this power can be re-crystallized from MeOH to yield an additional 35-40% of crystals over the evaporation. These crystals are crystallographically identical to the original batch. The total over all crystal yield is 85-90% in respect to Gallium. The refinement of the crystal structure of Ga101n3 without symmetry restrictions on occupation factors for the Ga and In atoms shows that the refined occupation factors of the Ga(1) and Ga(2) atoms are very close to those based on the crystal symmetry. The occupation factor of the In atom is less than the needed occupation factor of 1.0 based on symmetry. Refinement of the structure with the Ga and In atoms sharing the same In(1) position shows that the ratio of the occupation factors of Ga and In in this position is 1: 1, 163 i.e. the investigated compound is [Ga7Ga3In3(1l3-0H)6(1l-0H)18(H20)24](N03)15. The average In(Ga)-0(H20) distance in Galoln3, 2.073(6) A, is between the average Ga­ 0(H20) and In-0(H20) distances in Ga13 and [Ga7In6 clusters, 1.997(16) and 2.162(4) A, respectively. Crystal data/or Ga7In6 (Dave4): C6H96Ga7In6N15099, Mr= 3139.94. Colorless block, 0.15xO.15xO.07 mm, rhombohedral, space group R3 (no. 148), a=20.694(2), b=20.694(2), c=18.266(4) A, V=6774(2) A3, Z=3, Pcalcd=2.309 g'cm'3, f.!= 3.703 mm·l, F(000)=4620, 20max=56.50°, 16202 reflections collected, 3588 unique [Rint=0.0203], R indeces [1>2a(l)]: R1=0.0211, wR2=0.0582, GOF=1.035. Crystal data/or 3a(jtg63): C6H96G~.IIn3.9NI5099, Mr= 3045.23 Colorless block, 0.20xO.20xO.10 mm, rhombohedral, space group R3 (no. 148), a=20.4329(l0), b=20.4329(l0), c=18.4080(l8) A, V=6655.8(8) N, Z=3, pcalcd=2.279 g·cm·3, f.!= 3.86 mm'l, F(000)=4507, 20max=56.50°, 14035 reflections collected, 3500 unique [Rint=0.0176], R indeces [1>2a(l)]: R1=0.0237, wR2=0.0698, GOF=1.034. Crystal data/or Galoln3 (jtg65): C6H96GalO.3In2,7NI5099, Mr= 2991.11. Colorless block, 0.1OxO.1 OxO.05 mm, rhombohedral, space group R3 (no. 148), a=20.2946(12), b=20.2946(l2), c=18.456(2) A, V=6583.1(9) N, Z=3, pcalcd=2.239 g·cm·3, f.!= 3.96 mm' I, F(000)=4442, 20max=56.56°, 13757 reflections collected, 3460 unique [Rint=0.0217], R indeces [1>2a(l)]: R1=0.0326, wR2=0.0951, GOF=1.067. Crystal data for Gaulnl (jtg66): C6H96Ga11.9Inl.lN15099, Mr= 2918.95. Colorless block, 0.1 OxO.lOxO.05 mm, rhombohedral, space group R3 (no. 148), a=20.1387(l4), b=20.1387(l4), c=18.490(3) A, V=6494.3(l1) (2) A3, Z=3, pcalcd=2.239 g'cm'3, f.!= 4.08 164 mm-1, F(000)=4355, 28max=56A8°, 13623 reflections collected, 3412 unique [Rint=0.0317], R indeces [I>2a(1)]: R1=0.0328, wR2=0.0886, GOF=1.055. Crystal data/or Als1ns (dwjr21): C6H96Ah.7Ins.3Nls099, Mr= 2779.27. Colorless block, 0.18xO.14xO.08 mm, rhombohedral, space group R3 (no. 148), a=20A094(13), b=20A094(13), c=18.500(2) A, V=6673.8(10) N, Z=3, pcalcd=2.075 g·cm-3, f.t= 1.58 mm-\ F(000)=4166, 28max=56.50°, 15029 reflections collected, 3481 unique [Rint=0.0247], R indeces [I>2a(1)]: R1=0.0359, wR2=0.0960, GOF=1.134. X-ray diffraction experiments were carried out on a Bruker Smart Apex diffractometer at 153 K (Ga7In6) and 173 K (Ga9In4, Gal01n3, Ga12Inl, Als1ns) using MoKa radiation (A=0.71 070 A). Absorption corrections were applied by SADABS (Tminffmax = 0.762 (Ga7In6), 0.709 (Ga9In4), 0.769 (GaloIn3), 0.743 (Ga12Inl) and 0.825 (AIslns)). Crystals of Ga7In6, Ga9In4, Galoln3, Ga12Inl and Alslns are hexagonal and have the same space group R3 (no. 148). In all structures the M13 cations are on a3 axes. Two N03anions (in general positions) provide twelve N03 anions per the M13 cation. Three other N03 anions and solvent methanol molecules (in general positions as well) are highly disordered and randomly fill six other possible positions around the M13 cation. In all structures highly disordered N03 anions and solvent methanol molecules were treated by SQUEEZE. Corrections of the X-ray data by SQUEEZE (638 (Ga7In6), 642(Ga9In4), 596(Gal01n3), 620 (Ga12Inl) and 637 (AIslns) electron/cell) are close to the required value of 603 electron/cell for 9 N03 anions and 18 methanol molecules in the full unit cell. All non-H atoms were refined with anisotropic thermal parameters. H atoms in Ga7In6 were found on the difference F-map and refined with isotropic thermal 165 parameters. In other structures H atoms have not been taken into consideration. Refinements of the crystal structures of Ga7In6 without symmetry restrictions on occupation factors for the Ga and In atoms show that the refined occupation factors of the Ga(l) and Ga(2) atoms are very close to those based on the crystal symmetry. The found Ga(1)-O and Ga(2)-O distances in structures Ga7In6, Ga9In4, GalOIn3 and Ga12Intare close each other and the similar distances found in the Ga13 cation. It indicates that in all these structures the central M7 part of the M13 cations are formed by the Ga atoms only. The same situation was found for the structure of AlsIns where the central Ah core of the M13 cations are formed by the Al atoms only. In contrast refinement of occupation factors for the In atom in "Ga(3)-position" show that only in structure of Ga7In6 occupation factor for the In atom is close to required value of 1.0. In all other structure occupation factors for the In atoms in this position are less than the needed occupation factor of 1.0 based on symmetry. The final refinement of the structures of Ga9In4, GatOIn3, Ga12Inland 6 were done for a model with the Ga and In atoms sharing the same "Ga(3)­ position" position. It was found that based on single crystal X-ray diffraction data the ratios GalIn in the investigated compounds are Ga7In6 (Ga7In6), Ga9.1In3.9 (Ga9In4), GalO.3In2.7 (GatOIn3), Gall.9Inl.l (Ga12Int) and Ah.7Ins.3 (AlsIns). The found ratio are close to those found for these compounds by other methods (Table *). The values of the Ga(In)-O(H) and Ga(In)-OH2 distances found in these compounds are also indicate that in all compounds the Ga atoms in the "Ga(3)-position" positions only are replaced by the In atoms. The average In-O(H20) distance in Ga7In6, 2.162(4) A, is close to the distances found before in complexes with the Bi-O(H20) bond, for example 2.156 and 1.158 Ain 166 catena-[(1l2-0xalato-O,O',O',Olll)-bis(1l2-O',O",Olll)-tetraaqua-diindium dihydrato] 1• Decreasing the In ratio in the row Ga7In6 (Ga7In6), Ga9.lIn3.9 (Ga9In4), GalO.3In2.7 (Galoln3), Gall.9Inl.l (Ga12lnl), Ga13 is followed by decreasing the average In(Ga)­ O(H20) distances in this row: 2.162(4) A(Ga7In6), 2.105(6) A(Ga9In4), 2.074(7) A (Galoln3), 2.033(6) A(Ga12lnl) and 2.00(2) A(the Ga13 cation). The average In(AI)­ O(H20) distance in AIslns (AI7.7ms.3) is 2.156(7) A. The AI13° cluster cation has the similar structure as the Ga13° cluster cation where all the metal centers are octahedrally coordinated (Figure I). The M1(1l3-0H)6M6(1l2­ OH)6 core fragment (M = Ga, AI) forms a central core and six M1(H20)4 groups (Ml=In, Ga, AI) are connected to this core via two alkoxo (1l2-0H) bridges each group alternating above and below the plane and forming the third M-shell in the cluster cation. In all these structures the AI13 cluster cations have"3 symmetry as for the Ga13 cluster cation. In the all crystal structures the M13 clusters are surrounded by N03 anions and solvent water or methanol molecules forming O-R"O hydrogen bonds. Both H atoms of water molecules coordinated to the M (AI, Ga, In) atoms and the H atoms at the bridging 1l-0 atoms are involved in such H-bonds. 167 GalOln3 Table D.Ol. Crystal data and structure refinement for jtgr36. Identification code jtgr36 Empirical formula H72 Ga10 In3 N15 0102 Pormula weight 2956.39 Temperature 153(2) K Wavelength 0.71073 A Crystal system Rhombohedral Space group R-3 Unit cell dimensions a = 20.3239(4) A b = 20.3239(4) A c = 18.3780(7) A Volume 6574.2(3) A3 z 3 Density (calculated) 2.240 Mg/m3 Absorption coefficient 3.949 mm-1 P(OOO) 4350 Crystal size 0.14 x 0.12 x 0.06 mm3 Theta range for data collection 1.60 to 28.26°. Index ranges -26<=h<=23, -25<=k<=27, -23<=1<=20 Reflections collected 16312 Independent reflections 3478 [R(int) = 0.0227] Completeness to theta = 28.26° 95.6 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 1.000 and 0.835 Refinement method Pull-matrix least-squares on p2 Data I restraints I parameters 3478 116 I 242 Goodness-of-fit on p2 1.097 Pinal R indices [1>2sigma(I)] R1 = 0.0379, wR2 = 0.1117 R indices (all data) R1 = 0.0421, wR2 = 0.1154 Largest diff. peak and hole 1.976 and -1.003 e.A-3 168 Table D.02. Atomic coordinates (x 104) and equivalent isotropic displacement parameters (A2x 103) for jtgr36. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. x y z U(eq) Ga(1) 0 0 0 14(1) Ga(2) 1424(1) 1624(1) -37(1) 15(1) In(1) 3049(1) 1813(1) -944(1) 19(1) Ga(3) 3049(1) 1813(1) -944(1) 19(1) 0(1) 735(2) 1878(2) -493(2) 18(1) 0(2) 953(1) 580(1) -539(2) 16(1) 0(3) 2213(2) 2047(2) -754(2) 21(1) 0(4) 2714(2) 1517(2) -2017(2) 31(1) 0(5) 3600(2) 2315(2) 15(2) 34(1) 0(6) 2450(2) 726(2) -624(2) 21(1) 0(7) 3930(2) 1600(2) -1149(2) 37(1) 0(8) 3739(2) 2886(2) -1381(2) 29(1) N(15) 736(2) 2766(2) -1991(2) 26(1) 0(15) 1048(3) 3228(2) -2496(2) 49(1) 0(25) 846(3) 2220(3) -1935(2) 54(1) 0(35) 316(2) 2854(2) -1566(2) 37(1) N(25) 3819(3) 4155(3) 42(2) 40(1) 0(45) 3731(4) 4698(3) 147(3) 75(2) 0(55) 3530(2) 3592(2) 460(2) 48(1) 0(65) 4214(2) 4150(2) -495(2) 46(1) N(35) 895(12) 950(20) -2627(16) 250(18) 0(75) 1567(8) 1318(10) -2897(9) 120(5) 0(85) 360(7) 944(7) -2974(7) 86(4) 0(95) 844(10) 624(11) -2033(10) 132(7) 0(105) 5345(5) 2624(5) -1137(5) 55(2) 0(115) 5056(7) 2430(7) -2162(6) 75(3) 0(125) 1183(5) 837(5) -2012(5) 44(2) 169 Table D.03. Bond lengths [A] and O(7)-H(7B) 0.98(2) angles [0] for jtgr36. 0(8)-H(8A) 0.92(8) 0(8)-H(8B) 0.70(7) Ga(1)-0(2)#1 1.959(3) N(1S)-0(3S) 1.234(5) Ga(1)-0(2)#2 1.959(3) N(1S)-0(2S) 1.241(5) Ga(1 )-0(2)#3 1.959(3) N(1S)-O(1S) 1.245(5) Ga(1)-0(2)#4 1.959(3) N(2S)-0(4S) 1.219(7) Ga(1)-0(2) 1.959(3) N(2S)-0(5S) 1.254(6) Ga(1)-0(2)#5 1.959(3) N(2S)-0(6S) 1.275(6) Ga(2)-0(6)#1 1.908(3) N(3S)-0(9S) 1.254(17) Ga(2)-0(l) 1.911(3) N(3S)-0(8S) 1.255(16) Ga(2)-0(1)#4 1.913(3) N(3S)-0(7S) 1.285(17) Ga(2)-0(3) 1.914(3) N(3S)-0(12S) 1.34(2) Ga(2)-0(2) 2.059(2) 0(9S)-0(12S) 0.605(19) Ga(2)-0(2)#1 2.153(3) In(1)-0(6) 2.006(3) 0(2)#1-Ga(1)-0(2)#2 96.67(10) In(1)-0(3) 2.010(3) 0(2)#1-Ga(1)-0(2)#3 180.0(2) In(1)-0(5) 2.064(4) 0(2)#2-Ga(1)-0(2)#3 83.33(10) In(1)-0(7) 2.077(4) 0(2)#1-Ga(1)-0(2)#4 96.67(10) In(1)-0(4) 2.075(3) 0(2)#2-Ga(1)-0(2)#4 96.67(10) In(1)-0(8) 2.076(3) 0(2)#3-Ga(1)-0(2)#4 83.33(10) 0(1)-Ga(2)#1 1.913(3) 0(2)#1-Ga(1)-0(2) 83.33(10) O(1)-H(1) 0.99(2) 0(2)#2-Ga(1)-0(2) 180.0(3) 0(2)-Ga(2)#4 2.153(3) 0(2)#3-Ga(1)-0(2) 96.67(10) 0(2)-H(2) 0.99(2) 0(2)#4-Ga(1)-0(2) 83.33(10) 0(3)-H(3) 0.99(2) 0(2)#1-Ga(1)-0(2)#5 83.33(10) 0(4)-H(4A) 0.99(2) 0(2)#2-Ga(1)-0(2)#5 83.33(10) 0(4)-H(4B) 0.99(2) 0(2)#3-Ga(1)-0(2)#5 96.67(10) 0(5)-H(5A) 0.99(2) 0(2)#4-Ga(1 )-0(2)#5 180.00(18) 0(5)-H(5B) 0.99(2) 0(2)-Ga(1)-0(2)#5 96.67(10) 0(6)-Ga(2)#4 1.908(3) 0(6)#1-Ga(2)-0(1) 89.82(12) 0(6)-H(6) 0.97(2) 0(6)#1-Ga(2)-0(1)#4 95.82(12) O(7)-H(7A) 1.00(2) 0(1)-Ga(2)-0(1)#4 165.25(14) 170 0(6)#1-Ga(2)-0(3) 102.46(12) Ga(2)-0(2)-H(2) 136(6) 0(1)-Ga(2)-0(3) 98.00(12) Ga(2)#4-0(2)-H(2) 103(6) 0(1)#4-Ga(2)-0(3) 94.08(12) Ga(2)-0(3)-In(1) 129.06(15) 0(6)#1-Ga(2)-0(2) 166.21(11) Ga(2)-0(3)-H(3) 111(5) 0(1)-Ga(2)-0(2) 93.17(11) In(1)-0(3)-H(3) 117(5) O(1)#4-Ga(2)-0(2) 78.25(11) In(1)-0(4)-H(4A) 120(3) 0(3)-Ga(2)-0(2) 90.46(11) In(1)-0(4)-H(4B) 119(6) 0(6)#1-Ga(2)-0(2)#1 91.34(11) H(4A)-0(4)-H(4B) 93(6) 0(1)-Ga(2)-0(2)#1 75.97(11) In(1)-0(5)-H(5A) 124(6) 0(1)#4-Ga(2)-0(2)#1 90.25(11) In(1)-0(5)-H(5B) 140(5) 0(3)-Ga(2)-0(2)#1 165.01(11) H(5A)-0(5)-H(5B) 94(7) 0(2)-Ga(2)-0(2)#1 76.38(14) Ga(2)#4-0(6)-In(1) 133.08(15) 0(6)-ln(1)-0(3) 95.19(11) Ga(2)#4-0(6)-H(6) 104(4) 0(6)-ln(1)-0(5) 100.04(12) In(1 )-O(6)-H(6) 121(4) 0(3)-ln(1)-0(5) 92.89(13) In(1 )-0(7)-H(7A) 97(8) 0(6)-ln(1)-0(7) 86.27(13) In(1 )-0(7)-H(7B) 110(4) 0(3)-In(1 )-0(7) 178.54(13) H(7A)-0(7)-H(7B) 146(9) 0(5)-ln(1)-0(7) 86.91(15) In(1)-0(8)-H(8A) 109(5) 0(6)-In(1 )-0(4) 91.62(12) In(1 )-0(8)-H(8B) 120(5) 0(3)-ln(1)-0(4) 92.31(12) H(8A)-0(8)-H(8B) 112(7) 0(5)-ln(1)-0(4) 166.75(14) 0(3S)-N(1 S)-0(2S) 121.6(4) 0(7)-In(1 )-0(4) 87.59(14) 0(3S)-N(1S)-0(1S) 119.4(4) 0(6)-ln(1)-0(8) 171.91(13) 0(2S)-N(1S)-0(1S) 119.0(4) 0(3)-ln(1)-0(8) 91.50(12) 0(4S)-N(2S)-0(5S) 120.9(5) 0(5)-ln(1)-0(8) 84.12(14) O(4S)-N(2S)-0(6S) 120.6(5) 0(7)-In(1)-0(8) 87.04(14) 0(5S)-N(2S)-0(6S) 118.5(5) 0(4)-ln(1)-0(8) 83.57(14) 0(9S)-N(3S)-0(8S) 126.6(19) Ga(2)-0(1 )-Ga(2)#1 109.38(13) 0(9S)-N(3S)-0(7S) 115.2(17) Ga(2)-0(1)-H(1) 140(10) 0(8S)-N(3S)-0(7S) 118.2(17) Ga(2)#1-0(1)-H(1) 72(10) 0(9S)-N(3S)-0(12S) 26.6(10) Ga(1 )-0(2)-Ga(2) 101.77(12) 0(8S)-N(3S)-0(12S) 151(2) Ga(1 )-0(2)-Ga(2)#4 98.52(11) 0(7S)-N(3S)-0(12S) 89.8(14) Ga(2)-0(2)-Ga(2)#4 95.59(10) 0(12S)-0(9S)-N(3S) 85(2) Ga(1)-0(2)-H(2) 114(6) 0(9S)-0(12S)-N(3S) 68.4(18) 171 #1 x-y,x,-z #2 -x,-y,-z #3 -x+y,-x,z Symmetry transformations used to #4 y,-x+y,-z generate equivalent atoms: #5 -y,x-y,z Table D.04. Anisotropic displacement parameters (A2x 103) for jtgr36. The anisotropic displacement factor exponent takes the form: -2p2[ h2 a*2Ull + ... + 2 h k a* b* U12] Ull U22 U33 U23 U13 U12 Ga(1) 13(1) 13(1) 17(1) 0 0 7(1) Ga(2) 14(1) 14(1) 17(1) 0(1) 0(1) 7(1) In(1) 19(1) 17(1) 22(1) 2(1) 3(1) 10(1) Ga(3) 19(1) 17(1) 22(1) 2(1) 3(1) 10(1) 0(1) 16(1) 17(1) 20(1) 3(1) 1(1) 8(1) 0(2) 15(1) 15(1) 16(1) 0(1) 0(1) 7(1) 0(3) 20(1) 19(1) 23(1) 5(1) 6(1) 9(1) 0(4) 32(2) 30(2) 33(2) -4(1) -8(1) 17(1) 0(5) 37(2) 39(2) 29(2) 9(1) 4(1) 21(2) 0(6) 20(1) 19(1) 21(1) 3(1) 5(1) 9(1) 0(7) 44(2) 32(2) 42(2) 3(2) 8(2) 24(2) 0(8) 33(2) 32(2) 25(2) 1(1) 0(1) 18(2) N(1S) 31(2) 25(2) 24(2) 2(1) 0(1) 16(2) O(1S) 72(3) 37(2) 48(2) 22(2) 39(2) 35(2) 0(2S) 100(4) 63(3) 31(2) 17(2) 16(2) 66(3) 0(3S) 40(2) 41(2) 39(2) 19(2) 17(2) 27(2) N(2S) 42(2) 42(2) 30(2) 4(2) 1(2) 19(2) 0(4S) 113(5) 75(3) 64(3) 0(3) 7(3) 66(4) 0(5S) 50(2) 44(2) 37(2) 4(2) 14(2) 14(2) 0(6S) 51(2) 48(2) 31(2) 7(2) 10(2) 18(2) 172 Table D.OS. Hydrogen coordinates ( x 104) and isotropic displacement parameters (A2x 10 3) for jtgr36. x y z U(eq) H(1) 310(70) 1670(90) -850(70) 240(70) H(2) 930(60) 390(60) -1040(20) 120(40) H(3) 2280(50) 2530(30) -940(50) 100(30) H(4A) 2940(30) 1270(30) -2310(30) 38(15) H(4B) 2180(20) 1110(40) -2120(50) 110(30) H(5A) 3640(60) 2790(30) 210(50) 120(40) H(5B) 3750(50) 2170(50) 480(30) 80(30) H(6) 2440(40) 320(30) -910(30) 60(20) H(7A) 3660(70) 1060(30) -990(80) 180(60) H(7B) 4410(20) 2080(20) -1170(40) 60(20) H(8A) 3520(50) 2930(40) -1800(40) 70(20) H(8B) 3870(40) 3210(40) -1160(40) 38(18) Table D.06. Hydrogen bonds for jtgr36 [A and 0]. D-H...A d(D-H) d(H...A) d(D...A) «DHA) 0(1)-H(I)...0(2S) 0.99(2) 2.27(17) 2.721(5) 106(11) 0(1)-H(1)...0(6)#5 0.99(2) 2.21(16) 2.835(4) 119(13) 0(2)-H(2) ...0(9S) 0.99(2) 1.92(7) 2.759(17) 142(9) 0(2)-H(2)...0(12S) 0.99(2) 1.95(7) 2.752(9) 136(8) 0(3)-H(3)...0(lS)#6 0.99(2) 1.85(5) 2.762(4) 153(8) 0(4)-H(4A)...0(6S)#7 0.99(2) 1.78(2) 2.772(5) 176(5) 0(4)-H(4B)...0(12S) 0.99(2) 1.83(6) 2.700(10) 144(8) 0(4)-H(4B).. .0(7S) 0.99(2) 2.07(9) 2.696(16) 119(7) 0(5)-H(5A)...0(5S) 0.99(2) 1.81(3) 2.793(6) 168(9) 0(5)-H(5B)...0(1 S)#8 0.99(2) 1.96(7) 2.680(5) 128(6) 173 0(5)-H(5B)...0(2S)#8 0.99(2) 2.38(3) 3.343(5) 162(7) 0(6)-H(6).. .0(3S)#3 0.97(2) 1.85(2) 2.809(4) 170(7) 0(7)-H(7A) 0(5S)#4 1.00(2) 2.19(7) 3.115(5) 154(12) 0(7)-H(7A) 0(4S)#4 1.00(2) 2.70(14) 3.082(7) 103(9) 0(7)-H(7B) 0(1OS) 0.98(2) 1.65(4) 2.573(10) 156(7) 0(7)-H(7B) 0(11S) 0.98(2) 2.14(6) 2.773(12) 121(5) 0(8)-H(8A) 0(5S)#9 0.92(8) 2.05(8) 2.935(5) 160(7) 0(8)-H(8A) 0(3S)#6 0.92(8) 2.47(8) 2.993(5) 116(6) 0(8)-H(8B) 0(6S) 0.70(7) 2.08(7) 2.775(6) 177(7) Symmetry transformations used to generate equivalent atoms: #1 x-y,x,-z #2 -x,-y,-z #3 -x+y,-x,z #4 y,-x+y,-z #5 -y,x-y,z #6 -x+l/3,-y+2/3,-z-l/3 #7 x-y+1I3,x-l/3,-z-l/3 #8 -y+2/3,x-y+1I3,z+1I3 #9 -x+y+1I3,-x+2/3,z-l/3 174 Supplimental information for Heterometallic paper Experimental Section All chemicals were used as received: metal salts from Strem, N-nitroso-di-n­ butylamine from Tel, and nitrosobenzene from Aldrich. IR spectra were taken using a Nicolet Magna 550 spectrometer and UV-visible spectra were measured on a Hewlett Packard 8453 spectrometer. TGA was performed on a Thermal Analysis 2950. [Ga13Vt3-0HMJl-OH)18(H20)24] (N03)15 (1) Synthesized as previously described.2 Alternative organic additive. N-nitroso-di-n-butylamine (1.15 g, 7.26 mmol, 24 equivalents.) is added to gallium(III) nitrate (1.0 g, 3.91 mmol, 13 equivalents) in lOmL of methanol, as a homogeneous solution. The mixture was evaporated over 5 days at which point the methanol and nitrosoamine are no longer miscible and crystals begin to form on the sides and bottom of reaction vessel. After 4 more days the methanol completely evaporates giving a single liquid layer. The remaining oil is decanted and single crystals of 1 are washed with cold ethyl acetate (3x) and dried under air. This alternative method produces the identical GaB cluster in 85% yield with respect to gallium. The yield can be increased to nearly quantitative by precipitation of poorer quality crystals from the residual oil with cold ethyl acetate and re-crystallizing from methanol. [Ga7In6(Jl3-0HMJl-OH)18(H20)24](N03)15 (2) Gailium(III) nitrate (1.73 mg, 0.006 mmol, 1 equivalent) and indium(III) nitrate (24.7 mg, 0.082 mmol, 12 equivalents) are dissolved in 5 mL of methanol. Nitrosobenzene 175 (17.6 mg, 0.165 mmol, 24 equivalents) was dissolved in 2 mL of methanol, and the solutions were mixed together. The mixture was evaporated at room temperature over 10­ 12 days, yielding large single crystals of 2 in 25% yield with respect to indium nitrate. Alternate method. N-nitroso-di-n-butylamine (0.93g, 5.9 mmo124 eq.) was added to a solution of Ga(N03)3 (0.068g, 0.267 mmol, 1 eq.) and In(N03)3 (0.872g, 2.97 mmol, 12 eq.) in methanol, and formed a homogenous solution. The mixture was evaporated at room temperature over 10-12 days, affording 2 in 94% yield. Crystal data/or 2 (Dave4): C6H96Ga7In6Nls099, Mr= 3139.94. Colorless block, 0.15xO.15xO.07 mm, rhombohedral, space group R'3 (no. 148), a=20.694(2), b=20.694(2), c=18.266(4) A, V=6774(2) N, Z=3, rcalcd=2.309 gxcm·3, m= 3.703 mm·1, F(000)=4620, 20max=56.50°, 16202 reflections collected, 3588 unique [Rint=0.0203], R indeces [/>20(1)]: R1=0.0211, wR2=0.0582, GOF=1.035. X-ray diffraction experiments were carried out on a Broker Smart Apex diffractometer at 153 K (2) using MoKa radiation (1=0.71070 A). Absorption corrections were applied by SADABS (Tmi/fmax = 0.570 (1) and 0.762 (2). Crystal of 2, is hexagonal and have the same space group R'3 (no. 148). In all structures the M13 cations are on a'3 axes. Two N03 anions (in general positions) provide twelve N03 anions per the M13 cation. Three other N03 anions and solvent molecules (methanol in 2) are highly disordered and randomly fill six other possible positions around the M13 cation. In the crystal structure of 1 a disorder of N03 anions and solvent water molecules are more complex. In all structures highly disordered N03 anions and solvent methanol molecules 176 were treated by SQUEEZE.3 Corrections of the X-ray data by SQUEEZE are 353 and 638 electron/cell, respectively for 1 and 2; to the required values are 349 electron/cell for 9 N03 anions and 7 water molecules in 1 and 603 electron/cell for 9 N03 anions and 18 methanol molecules in 2. All non-H atoms were refined with anisotropic thermal parameters except the atoms of the disordered N03 anion. In all structures H atoms were found on the difference F-map and refined with isotropic thermal parameters except those in disordered water molecules, which were not taken into consideration. Refinements of the crystal structures of 2 without symmetry restrictions on occupation factors for the Ga and In atoms show that the refined occupation factors of the Ga(l) and Ga(2) atoms are very close to those based on the crystal symmetry. The found Ga(I)-O and Ga(2)-O distances in structure 2 is similar distances found in the GaB cation [*]. It indicates that in all these structures the central M7 part of the M13 cations are formed by the Ga atoms only. In contrast refinement of occupation factors for the In atom in "Ga(3)-position" show that only in structure of 2 occupation factor for the In atom is close to required value of 1.0. In all other structure occupation factors for the In atoms in this position are less than the needed occupation factor of 1.0 based on symmetry. The values of the Ga(In)-O(H) and Ga(In)-OH2 distances found in these compounds are also indicate that in all compounds the Ga atoms in the "Ga(3)-position" positions only are replaced by the In atoms. In the all crystal structures the M13 clusters are surrounded by N03 anions and solvent water or methanol molecules forming O-H"O hydrogen bonds Both H atoms of water molecules coordinated to the M (Ga, In) atoms and the H atoms at the bridging m-O atoms are involved in such H-bonds. The average ----------- -----_._--- - ---- 177 In(Ga)-O(H20) distance in Ga13 and [G~In6 clusters, 1.997(16) and 2.162(4) A, respectively. These distances are close to the distances found before in complexes with the Bi-O(H20) bond, for example 2.156 and 1.158 A in catena-[(jt2-0xalato­ O,O',O',O"')-bis(jt2-0',O",O"')-tetraaqua-diindium dihydrato].' Supporting information available These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ, UK; fax: (+44)1223-336-033; or deposit@ccdc.cam.ac.uk). 178 Figure D.02 Ga7In6 179 Crystal Data from Ga7In6 Heterometallic Anderson-like nanocluster. Table D.07. Crystal data and structure refinement for dav4. Identification code dav4 Empirical formula C6 H96 Ga7 In6 N15 099 Pormula weight 3139.94 Temperature 153(2) K Wavelength 0.71073 A Crystal system Rhombohedral Space group R-3 Unit cell dimensions a = 20.694(2) A a= 90°. b = 20.694(2) A c = 18.266(4) A Volume 6774.2(16) A3 Z 3 Density (calculated) 2.309 Mg/m3 Absorption coefficient 3.703 mm-1 P(OOO) 4620 Crystal size 0.15 x 0.15 x 0.07 mm3 Theta range for data collection 1.59 to 28.25°. Index ranges -27<=h<=27, -26<=k<=20, -22<=1<=24 Reflections collected 16202 Independent reflections 3588 [R(int) = 0.0203] Completeness to theta = 28.25° 96.3 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 1.000 and 0.762 Refinement method Pull-matrix least-squares on p2 Data I restraints I parameters 3588/12 I 213 Goodness-of-fit on p2 1.035 Pinal R indices [1>2sigma(l)] Rl = 0.0211, wR2 = 0.0582 R indices (all data) Rl = 0.0222, wR2 = 0.0588 Largest diff. peak and hole 1.015 and -0.438 e.A-3 180 Table D.08. Atomic coordinates (x 104) and equivalent isotropic displacement parameters (A2x 103) for dav4. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. x y z U(eq) Ga(1) 6667 3333 8333 20(1) Ga(2) 6462(1) 1728(1) 8370(1) 20(1) In(1) 7880(1) 1517(1) 9290(1) 22(1) 0(1) 7031(1) 2758(1) 8875(1) 21(1) 0(2) 7392(1) 2196(1) 7849(1) 23(1) 0(3) 8375(1) 2630(1) 8970(1) 26(1) 0(4) 6792(1) 1295(1) 9101(1) 25(1) 0(5) 7484(1) 407(1) 9717(1) 27(1) 0(6) 8999(1) 1724(1) 9480(1) 39(1) 0(7) 7923(1) 1001(1) 8272(1) 33(1) 0(8) 7870(1) 1789(1) 10428(1) 41(1) N(1S) 7414(1) 1304(1) 6346(1) 29(1) O(1S) 7767(2) 1176(1) 5877(1) 57(1) 0(2S) 6986(1) 798(1) 6765(1) 39(1) 0(3S) 7496(1) 1943(1) 6383(1) 50(1) N(2S) 9188(1) 2884(1) 1706(1) 40(1) 0(4S) 8656(2) 2973(2) 1819(2) 74(1) 0(5S) 9749(1) 3190(1) 2117(1) 55(1) 0(6S) 9180(1) 2473(1) 1195(1) 47(1) Table D.09. Bond lengths [A] and angles [0] for dav4. Ga(1 )-0(1)#1 1.9656(15) Ga(1)-O(1) 1.9656(15) Ga(1)-0(1)#2 1.9657(15) Ga(1)-0(1)#3 1.9657(15) Ga(1)-0(1)#4 Ga(1 )-0(1)#5 Ga(2)-0(3)#4 Ga(2)-0(2)#4 Ga(2)-0(4) Ga(2)-0(2) Ga(2)-0(1) 1.9657(15) 1.9657(15) 1.9075(16) 1.9109(15) 1.9117(16) 1.9184(15) 2.0673(15) 181 Ga(2)-0(1 )#4 2.1589(15) O(1)#2-Ga(1)-O(1)#3 96.89(6) In(1)-0(3) 2.0823(15) O(1)#1-Ga(1)-O(1)#4 96.89(6) In(1)-0(4) 2.0903(15) 0(1)-Ga(1)-0(1)#4 83.11(6) In(1)-0(8) 2.1565(19) 0(1)#2-Ga(1)-0(1)#4 179.998(1) In(1)-0(5) 2.1620(16) 0(1 )#3-Ga(1)-0(1)#4 83.11(6) In(1)-0(6) 2.1627(18) O(1)#1-Ga(1)-O(1)#5 96.89(6) In(1)-0(7) 2.1668(17) O(1)-Ga(1)-O(1)#5 83.11(6) 0(1)-Ga(2)#5 2.1590(15) 0(1)#2-Ga(1)-0(1)#5 83.11(6) O(1)-H(1) 1.000(19) O(1)#3-Ga(1)-O(1)#5 180.00(8) 0(2)-Ga(2)#5 1.9109(15) 0(1 )#4-Ga(1 )-0(1)#5 96.89(6) 0(2)-H(2) 0.986(18) 0(3)#4-Ga(2)-0(2)#4 90.16(7) 0(3)-Ga(2)#5 1.9074(16) 0(3)#4-Ga(2)-0(4) 101.79(7) 0(3)-H(3) 0.970(19) 0(2)#4-Ga(2)-0(4) 96.80(7) 0(4)-H(4) 0.976(19) 0(3)#4-Ga(2)-0(2) 95.14(7) 0(5)-H(5A) 0.949(19) 0(2)#4-Ga(2)-0(2) 166.14(8) 0(5)-H(5B) 0.949(19) 0(4)-Ga(2)-0(2) 94.64(7) 0(6)-H(6A) 0.97(2) 0(3)#4-Ga(2)-0( 1) 165.87(7) 0(6)-H(6B) 1.00(2) 0(2)#4-Ga(2)-0( 1) 94.09(6) 0(7)-H(7A) 0.945(19) 0(4)-Ga(2)-0(1) 91.09(6) 0(7)-H(7B) 0.940(18) 0(2)-Ga(2)-0(1) 77.87(6) 0(8)-H(8A) 0.957(19) 0(3)#4-Ga(2)-0(1)#4 91.88(6) 0(8)-H(8B) 0.99(2) 0(2)#4-Ga(2)-0(1)#4 75.79(6) N(1S)-0(2S) 1.239(3) 0(4)-Ga(2)-0(1)#4 164.55(7) N(1S)-O(1S) 1.238(3) 0(2)-Ga(2)-0(1)#4 91.21(6) N(1S)-0(3S) 1.248(3) O(1)-Ga(2)-0(1)#4 76.17(8) N(2S)-0(4S) 1.221(3) 0(3)-In(1 )-0(4) 94.40(6) N(2S)-0(5S) 1.257(3) 0(3)-In(1 )-0(8) 92.62(7) N(2S)-0(6S) 1.257(3) 0(4)-In(1 )-0(8) 93.83(7) 0(3)-In(1)-0(5) 172.72(6) 0(1)#1-Ga(1)-0(1) 179.998(1) 0(4)-In(1)-0(5) 91.85(6) O(1)#1-Ga(1)-O(1)#2 83.11(6) 0(8)-In(1)-0(5) 83.23(8) O(1)-Ga(1)-O(1)#2 96.89(6) 0(3)-In(1)-0(6) 86.56(7) 0(1)#1-Ga(1)-0(1)#3 83.11(6) 0(4)-In(1)-0(6) 178.87(7) 0(1)-Ga(1)-0(1)#3 96.89(6) 0(8)-In(1)-0(6) 86.72(8) 182 0(5)-In(1)-0(6) 87.23(7) 1I(5A)-0(5)-1I(5B) 110(4) 0(3)-In(1 )-0(7) 100.66(7) In(1)-O(6)-1I(6A) 119(4) 0(4)-In(1 )-0(7) 93.14(7) In(1)-0(6)-1I(6B) 129(4) 0(8)-In(1)-0(7) 164.48(8) 1I(6A)-0(6)-1I(6B) 105(5) O(5)-In(1)-0(7) 82.70(7) In(1)-0(7)-1I(7A) 116(3) 0(6)-In(1)-0(7) 86.09(7) In(1 )-0(7)-1I(7B) 109(2) CJa(I)-0(1)-CJa(2) 101.95(7) 1I(7A)-0(7)-1I(7B) 119(3) CJa(1 )-0(1 )-CJa(2)#5 98.78(6) In( 1)-0(8)-1I(8A) 121(3) CJa(2)-0(1 )-CJa(2)#5 95.78(6) In(1)-0(8)-1I(8B) 100(5) CJa(I)-O(I)-lI(l) 122(2) 1I(8A)-0(8)-1I(8B) 117(6) CJa(2)-0(1)-1I(1) 115(2) 0(2S)-N(1 S)-O(1 S) 119.7(2) CJa(2)#5-0(1)-1I( 1) 118(2) 0(2S)-N(1 S)-0(3S) 121.5(2) CJa(2)#5-0(2)-CJa(2) 109.95(7) 0(1 S)-N(1 S)-0(3S) 118.8(2) CJa(2)#5-0(2)-1I(2) 122.7(19) O(4S)-N(2S)-0(5S) 119.9(3) CJa(2)-0(2)-1I(2) 117.6(19) 0(4S)-N(2S)-0(6S) 121.3(3) CJa(2)#5-0(3)-In( 1) 131.83(8) 0(5S)-N(2S)-0(6S) 118.7(2) CJa(2)#5-0(3)-1I(3) 114(3) In(1)-0(3)-1I(3) 112(3) Symmetry transformations used to CJa(2)-0(4)-In(1) 127.57(8) generate equivalent atoms: CJa(2)-0(4)-1I(4) 106(3) #1 -x+4/3,-y+2/3,-z+5/3 #2 -y+l,x-y,z In(1)-0(4)-1I(4) 121(3) #3 -x+y+l,-x+l,z In(1)-O(5)-1I(5A) 113(3) #4 y+1/3,-x+y+2/3,-z+5/3 #5 x­ In(1)-0(5)-1I(5B) 116(3) y+1/3,x-l/3,-z+5/3 Table D.lO. Anisotropic displacement parameters (A2x 103) for dav4. The anisotropic displacement factor exponent takes the form: -2p2[ h2 a*2Vll + ... + 2 h k a* b* V12 ] V11 V22 V33 V23 VB V12 CJa(1 ) 17(1) 17(1) 25(1) o o 9(1) CJa(2) 16(1) 18(1) 26(1) 0(1) -1(1) 8(1) In(1) 20(1) 18(1) 25(1) -1(1) -2(1) 8(1) 0(1) 21(1) 19(1) 24(1) 1(1) -1(1) 10(1) 0(2) 20(1) 21(1) 26(1) -2(1) 2(1) 9(1) 183 0(3) 24(1) 19(1) 32(1) 1(1) -5(1) 9(1) 0(4) 20(1) 21(1) 33(1) 2(1) -2(1) 8(1) 0(5) 27(1) 25(1) 28(1) 5(1) 2(1) 12(1) 0(6) 21(1) 37(1) 52(1) -7(1) 1(1) 9(1) 0(7) 41(1) 29(1) 27(1) 1(1) 3(1) 17(1) 0(8) 30(1) 46(1) 32(1) -13(1) 2(1) 9(1) N(1S) 38(1) 29(1) 23(1) -3(1) -3(1) 20(1) O(1S) 92(2) 44(1) 52(1) 19(1) 40(1) 48(1) 0(2S) 45(1) 29(1) 40(1) -2(1) 12(1) 17(1) 0(3S) 83(2) 31(1) 39(1) -4(1) 7(1) 31(1) N(2S) 35(1) 47(1) 35(1) -1(1) -1(1) 17(1) 0(4S) 55(2) 118(2) 69(2) 0(2) 4(1) 59(2) 0(5S) 33(1) 69(2) 51(1) -28(1) -6(1) 15(1) 0(6S) 43(1) 58(1) 29(1) -11(1) -6(1) 16(1) Table D.ll. Hydrogen coordinates ( x 104) and isotropic displacement parameters (A2x 10 3) for dav4. x y z U(eq) H(1) 7040(20) 2740(20) 9422(10) 60(11) H(2) 7375(18) 2114(18) 7316(10) 46(9) H(3) 8765(19) 2960(20) 9310(20) 82(14) H(4) 6361(19) 807(16) 9210(30) 96(16) H(5A) 7140(20) 290(20) 10111(17) 75(13) H(5B) 7280(20) 15(19) 9370(20) 84(14) H(6A) 9390(20) 2020(30) 9130(30) 120(20) H(6B) 9160(40) 1400(30) 9720(30) 160(30) H(7A) 7471(16) 585(18) 8110(20) 82(14) H(7B) 8209(16) 1376(15) 7930(15) 41(8) H(8A) 8324(17) 2050(20) 10700(20) 81(14) H(8B) 7550(40) 2020(50) 10410(50) 230(50) 184 Table D.12. Hydrogen bonds for dav4 [A and 0]. D-H...A d(D-H) d(H...A) d(D...A) «DHA) 0(2)-H(2)...0(3S) 0.986(18) 1.784(19) 2.758(3) 169(3) 0(3)-H(3)...0(2S)#5 0.970(19) 1.86(2) 2.825(2) 175(4) 0(4)-H(4)...0(1S)#6 0.976(19) 1.81(2) 2.774(3) 167(5) 0(5)-H(5A)...0(5S)#7 0.949(19) 2.06(3) 2.921(3) 150(4) 0(5)-H(5A)...0(2S)#6 0.949(19) 2.30(4) 2.983(2) 128(3) 0(5)-H(5B)...0(6S)#8 0.949(19) 1.84(2) 2.778(3) 168(4) 0(6)-H(6A)...0(4S)#9 0.97(2) 2.12(3) 3.044(4) 157(5) 0(6)-H(6A)...0(5S)#9 0.97(2) 2.27(4) 3.085(3) 141(4) 0(7)-H(7A)...0(5S)#8 0.945(19) 1.86(2) 2.807(3) 175(4) 0(7)-H(7B)...0(1S)#7 0.940(18) 1.759(19) 2.683(3) 167(3) 0(8)-H(8A)...0(6S)#1O 0.957(19) 1.78(2) 2.736(3) 175(4) Symmetry transformations used to generate equivalent atoms: #1 -x+4/3,-y+2/3,-z+5/3 #2 -y+1,x-y,z #3 -x+y+1,-x+1,z #4 y+1I3,-x+y+2/3,-z+5/3 #5 x-y+1/3,x-1I3,-z+5/3 #6 -y+2/3,x-y-2/3,z+1I3 #7 -x+5/3,-y+1I3,-z+4/3 #8 x-y,x-1,-z+1 #9 -y+4/3,x-y-1I3,z+2/3 #10 x,y,z+l --------- ------ 185 10000.0 9000.0 BOOO.O 7000.0 ~OOO.O .;;; c: ~5000.0 4000.0 3000.0 2000.0 1000.0 0.0 h,k.I-2.0.-1 10.0 20.0 30.0 40.0 2lhela Figure D.03. Predicted powder spectra of Ga7In6. Sample: AAT_l_40 File: C: ...\CrystaIClearlAAT_1_40 Size: 20,6720 mg TGA Operator: TLA Method: JTG Run Dale: 15-0ct-07 13:06 120 . 100 ­ ---- ... 19.58% (4.087mg) ~ .E 80-; .!2' ~ 26,79% (5.591mg) 60 40 _r_----___,-----__r--~--_r_----___,r_----__r--~-_____1 o 100 200 300 400 SOO 600 Temperature ee) Universal V2.6D TA Instruments Figure D.04. TGA thermogram of Ga7In6' 50.0 186 APPENDIXE SUPPLEMENTAL INFORMATION FOR ToF-SIMS ANALYSIS Isotope distribution of Ga clusters. 100.00 • 15.00 2J c -l§ c ::> D « 50.00 Q) .2 i'il Qj a: '#. 25.00 o -r===rl=====;====~~=====! > 65.0 67.0 6,9.0 71.0 73.0 75.0 Mass Figure E.Ol Pictorial representation of the isotope distribution of one metal center. Table E.Ol Statistical distribution of one metal center. # f .1etal meia 7J(Ja 1 ratio ~l ofeach 60. 08 39.892 rna 68.926 70.925 187 100.00 75.00 ~ ~ "1;J c ~ Q) 50.00 .<'; 10 ;f #. 25.00 o'=;:::::::=;:::::::::::::;;:::::::=;==;:~ 133.0 135.0 137.0 139.0 Mass Figure E.02. Pictorial representation of the isotope distribution of two metal centers. Table E.02. Statistical distribution oftwo metal centers. # f~letal 2 rD(Ja 2 7lQ, 2 r ti 2 % of each 36.30 - 7.957 5.914 lUS 37.85 39.85 .85 141.0 143.0 145.0 188 100.00 "/5.00 . ~ c '0 '" c ~ 50.00 ~ 202.0 205.0 208.0 211.0 214.0 217.0 Mass Figure E.03. Pictorial representation of the isotope distribution of three metal centers. Table E.03. Statistical distribution of three metal centers. # of~1etal 3 lZI(ja 3 2 .)71(ja ... 3 ~ ratio 1 .\ 3 % ofeach 21.7 7 3.239 28.696 6.348 lass 206.78 208.78 2 0.77 2 2.77 189 100.00 75.00 ~ 'E '" ::i! 50.00 .g! al Qj a: ,,~ 25.00. J o .1;:i====;,===;:~~==!.........::;======f:1==~*==:;:::::=~===;:===r-.,.i> 272.0 274.0 276.0 278.0 280.0 282.0 284,0 286.0 Mass Figure E.04. Pictorial representation of the isotope distribution of four metal centers. Table E.04 Statistical distribution of four metal centers. fI fMet, 1 4 me 3 2 7l() 2 3 4 r fo 1 4 4 1 C/ ofeach 3.054 3 .653 3 97 5.263 2532 I 1 _5 275.70 277.70 279.70 28 .70 283.70 190 100.00 75.00 50.00 "]!r=i==;:===;=:;=,===;:~r===:# I f >i • 339.0 342.0 345.0 348.0 351.0 354.0 357.0 Mass Figure E.OS. Pictorial representation of the isotope distribution of five metal centers. Table KOS. Statistical distribution of five metal centers. 1# f eta] 5 ril(J 5 4 3 2 '1(}, 1 2 ). 5 r 5 () 0 5 % feach 7.8 6 26.037 3 560 22.936 7.6 .010 11, s 34 .63 346.63 3 8.63 350.63 352.62 35 .62 191 100.00 75.00 50.00 25.00 o ~;:::=i:::;:=;:=:;==,~A.~\.~==;!.....4=i~~il\~,~i=;::::::=.,. 408.0 411.0 414.0 417.0 420.0 423.0 426.0 Mass Figure E.06 Pictorial representation of the isotope distribution of six metal centers. Table E.06 Statistical distribution of six metal centers. # of Metal (, lII(Ja (, 5 4 3 2 I 7l(J 1 2 3 5 6 ratio 6 15 20 5 6 1 l,;'c ofeach 4.7162 18:78 3 L. 6 27.573 3.725 3.6434 0.403 III s 355 4 5.55 41755 4 955 2 .55 423.55 425.55 192 100.00 . 75.00 ~ ~ c :::> ..0 ...: 50.00 .~ '" !i! a; a: f;i?' 25.00 o -{;:::::=;::::=;:::==;::==;=;!!!:=~ 477.0 461.0 465.0 469.0 493.0 497.0 Mass Figure E.07 Pictorial representation of the isotope distribution of seven metal centers. Table E.07 Statistical distribution of seven metal centers. If of Metal 7 fil(Ja 7 6 5 4 3 2 71(ja I 2 3 5 6 7 ratio I 7 21 35 35 21 7 I ~{., ofeach 2.8348 13.17 26.221 29.004 19249 7.665 .6957 0.1608 m .S 482.48 484.48 486.48 488.48 490.&8, 492.47 494.47 4%.47 193 ,. ,­100.00 75.00 ~ c ~ :::l ~ Q) 50.00 ­ '§ &! #. 25.00 o "'T===T::::::::;==;:=r=;!=I\::!::;=(=:!:;==¢::::::i~9=~~"!:r=~A=;:2:::r=A:::::;=;:::::::::::;::=-,. 546.0 550.0 554.0 558.0 562.0 566.0 Mass Figure E.08. Pictorial representation of the isotope distribution of eight metal centers. Table E.08. Statistical distribution of eight metal centers. Ii ofMetals 8 "'Ga 8 7 6 5 4 3 2 1 71Ga 1 2 3 4 5 (. 7 8 ratio 1 8 28 56 70 56 28 8 I 0;' of each 1.704 9.0469 21.015 27.894 23.14 12286 4.077 0.7731 0,0641 mass 55 .4 553.4 555.4 557.4 559.4 56 .4 563.4 565,4 567.4 ------- -- 194 Figure E.09 Pictorial representation of the isotope distribution of nine metal centers. Table E.09. Statistical distribution of nine metal centers. 1# of~fctaJs 9 "'Ga 9 8 7 6 5 4 3 2 1 "Ga 1 2 3 4 5 6 7 8 9 ratio 1 9 36 84 126 126 84 36 9 1 % of each 1.0242 6.1177 16.241 25.15 25.037 [6.616 735 8 2.0911 0.3469 0.0256 mass 62033 622.33 624.33 626.33 628.33 630.33 632.32 634.32 636.32 638.32 100.00 . 75.00 0 '" c 'U '" C ~. 50.00 . '" ~ c: ~ 50.00 .:!: '" !l ex:'" 'if.. 2S.00 _ ~ AJ \. .J ... A .../",O' i i > 154.0 756.0 '162.0 766.0 770.0 '/74.0 7'16.0 Mass Figure E.11 Pictorial representation of the isotope distribution of eleven metal centers. Table E.1l. Statistical distribution of eleven metal centers. 1/ ofMelals II "'Ga 11 10 9 8 7 6 5 4 3 2 I "Cia I 2 3 4 5 6 7 8 9 10 11 ratio 1 11 55 165 330 462 462 330 165 55 II 1 % ofeach 037 2.7015 8.9645 17.848 23.691 22.012 14.609 6.9254 22981 05084 0.0675 0.0041 mass 758.18 760.18 762.18 764.18 766.18 768.18 770.18 772.18 774.17 776.17 778.17 780.17 196 100.00 75.00 fl c "C '"C ::l .0 =S S 6 202 oo R= a=OEt p' p ' ;J"~ b=OBn '" N 'N -(NY I b 1. K,CO, TIlFlwaI'" • I:' THF DMAP, EDCI I b ~ ~ 2. Acid workup ~ ~ 5· HN.Jl- ~ 1s LJ '" I b N 1\ 1{­ SyNr 6c S 0 6d6a,b Scheme G.3. Synthetic scheme to make the L' nanocages. 19,31 ------------- 208 1; cap wi trpn (4 cquiv.2../' a,b R = OEt, OSnI~ HZN N)°2 R cR=OH 'N 9HZ ~N SY 2/3 Zn(BF4)2 .. d - II 2; dcmetallatc HN/'...,S:~ \......J Rx0 organic nanocage [L'] R 70r 8 oo 10 Scheme G.4. Self-assembly of ligands 5 or 6 to form the template organic nanocage 7 and 8. The starting pyridine ring for this synthesis can be substituted with either a carboxylic acid or an ester (ethyl or benzyl) in the 3 position. These different groups affect the yields of the first step. The rigid diamine spacer has also been varied, using benzidine, 3 (4-4' -diaminobiphenyl) and 4 (4-4"-diaminoterphenyl) modification of the ligand at the distal end and the 3 position of the pyridine ring (Scheme G.3). Figure G.2 shows the models of complexes that we wish to make as the carboxylic acid, the capped ester and the dovetailed organic nanocage. Computer modeling shows that the ester is far enough away from the Schiff base binding motif not to interfere in the complexation with the metal (Figure G.2A).32 Figure G.2B addresses the sterics of the cap and Figure G.2C is the goal of phase one: the demetallated organic nanocage. 209 organic nanocagc [L'j Figure G.2. Computer model with MM3 of target M4L6 tetrahedron, capped M4L' and then de-metallated L' complexes.32 Ligand Synthesis The target ligands of 5d and 6d, substituted with activated ester groups, pose a better likelihood of yielding the tetrahedron template. This would avoid having to remove all 12 ester groups on complex 7a,b and 8a,b simultaneously and provides tetrahedron complex 7d ready to be capped with the amine without changing a functional group. The first target ligand, Sa, has an ethyl protected carboxylic acid at its distal ends. The first step of the synthesis (Scheme G.3) proceeds with an acceptable yield of 11 to 23% .31 The acylation reaction works on a variety of ester R groups (R= OR, OEt or OBn). The different R groups affect the yield and solubility of the ligands after the condensation reaction to yield ligands Sa, 5b, 6a and 6b. Although TLC of the acylation reaction shows that only one species is isolated from column chromatography, NMR reveals 6: 1 ratio of compounds 2a and 11, respectively is obtained (Figure G.3A). Overall crude yields can be increased by shortening the reaction time to limit the 210 formation of side product 11. Repeated attempts to separate the desired product from the side product gave the same result so the mixture was carried onto the following step, condensation with 3. Figure G.3. Acylation side products 11a & 12a from the formation of ketone 2a. The condensation reaction of 2a with 3 (Scheme G.5) is done in absolute ethanol by adding two equivalents of ketone, 2a, to one equivalent of benzidine, 3, at reflux with catalytic acetic acid for four hours to provide Sa in 86% yield. Ligand Sa precipitates out of the reaction mixture, helping with yield and purification. Washing with cold methanol removes unreacted starting materials. Analytically pure ketone, 2a, is not needed for the condensation reaction because the disubsituted ketone (l1a) can easily be removed after the condensation reaction to yield pure Sa (Figure G.3A and C) by precipitation. Many different reaction conditions have been tried to optimize the yield of 4a (see experimental).33,34 Increasing the ratio of ketone to benzidine to five to one should drive the reaction to completion in benzidine and thus make the column chromatographic separation easier (3 and Sa have very similar Rr values). Unreacted 2a can then be recovered and reused. Current yields in absolute ethanol with the acetic acid catalyst are 211 in excess of 85% analytically pure ligand Sa. Single crystal x-ray structure confirms the structure of Sa as the free base ligand (Figure G.4). Figure GA. Ortep of Sa single crystal structure, and packing pictures. Benzidine, 3, and 4-4"-terphenyldiamine, 4, both crystallize with the rings completely planar; this is not the lowest energy confirmation that we would expect, but it does allow for greater edge to face interaction between adjacent molecules in the cell. The angle of the plane of one biphenyl to the adjacent is about 70°. 35 The biphenyl portion of Sa crystallizes in a planar fashion as well, but it places the adjacent ligands in a complete 90° edge to face arrangement. This increases the strength of the edge to face interactions and it stacks the pyridine rings face to face with an offset angle. This packing in the solid state may help to explain the unusual behavior of Sa in DMSO solution. (Figure G.5) Ligand Sa has an expected spectrum in CDCI3, but when dissolved in DMSO it behaves quite differently (Figure G.5), suggesting it forms a not-well-understood, 212 concentration-dependent oligomer in DMSO. This issue is not only concentration dependent, but also solvent dependent. ppm (1) Figure G.S. IH NMR spectra of ligand Sa in DMSO at various concentrations, showing the concentration dependent behavior. At 1/16 concentration mostly monomer appears to be present. The same batch of pure ligand is sequentially dissolved in one solvent, analyzed, dried down and resuspended in a different NMR solvent. The ligand, in going from chloroform to DMSO, shows first the simple then the complex spectra, then back to a clean spectrum, again in chloroform (Figure G.6). 213 DMf I 9.0ppm (t1) Figure G.6 'H NMR of ligand Sa showing the solvent and concentration effects are reversible. Concurrently ligand 6b was synthesized by the same procedure.36 Ligand 6b has very poor solubility in all solvents. The same route from intermediate ketones 2a and 2b also synthesized the two crossover ligands 5b and 6a. All four ligands are concurrently being carried on for self-assembly and de-protection reactions. Deprotection Two different routes for deprotection have been explored. The first route was to deprotect ketone 2b with potassium carbonate into the carboxylic acid 2c then activate with 2-mercaptothiazoline to yield the activate ester 2d for capping and condensation I 8.0 214 reactions.37 This same route is being explored to convert ligands 5d and 6a into 5d and 6d. The second route under investigation involves heating of Sa in DMSO/water solution at 95°C with potassium hydroxide. By NMR spectroscopy both reactions appear to have removed the ethyl groups, although the ligand has not yet been purified. Self-assembly ofLigands Because of the unusual behavior of Sa in DMSO, metallation and further studies will be attempted in DMF. Ligand Sa has been heated with two-thirds equivalents of Zn(BF4)2 or Zn(OTf)2 to yield a new compound that is currently being characterized in d7-DMF. By IH NMR spectroscopy there are new peaks that do not correspond to any of the starting materials. It seems that both the tetrafluoroborate and the triflate counter ions yield similar results, although it appears to take longer for the reaction to occur with the triflate salt.38•39 215 ppm (t1?-0 ..J.~ I I 8.0 Figure G.7. Time points of Sa in DMF with 2/3rds equivalents of Zn(BF4)2' A different IH NMR spectrum can be obtained on multi milligram scale by running the reaction in a Schlenk tube. A pasty solid is obtained by heating 2 equivalents of ligand Sa with 1 equivalent of Zn(BF4)2 in DMF at 60°C for 16 hours, reducing the volume, and precipitating with ethyl acetate. Unreacted ligand was extracted by washing with ethyl acetate. The paste was dried in vacuo. Other metallation reactions with ligand Sa and other metals are cUlTently being tried. 216 I ppm {t1} 9.0 Figure G.8. Time points of Sa in DMF with 2/3rds equivalents of Zn(OTf)2. Metallation reactions are being tried with the other isolated and characterized ligands (5b, 6a and 6b). Metallation will also be attempted on deprotected acid ligands (5c and 6c) as well as the target thiazoline activated esters (5d and 6d when they are prepared). Ligands 6a and 6b exhibit very poor solubility. Heating and cooling to room temperature causes the ligand crash out very quickly. The addition of Zn(BF4)2 to the solution helps keep the ligands in solution. Many other attempts at crystalization and characterization of the complex are in progress. 217 Concurrent Work on Alternate schemes Activated Esters Anticipating that the capping of the templated cage will be very difficult in high yields; possible solutions to this problem are to increase the yield or to change the order of the reactions to do the more difficult reaction earlier. The first method we are trying is to activate the ester to facilitate the formation of 12 amide bonds simultaneously. The main goal is to get to ligand Sd or 6d from Scheme 3. This is a modification of the project as it was unfolding eR 1'<:: ""N Ie S HN~ lj -------. OCM,DCC, DMAP s')-s(5J 1'<:: ""N Id ° ll.. C2iL10 Mol. WI.: 44.05 - -------­ -------. H2S04 FeS04 I-butyl peroxide @ 5-IO'C 15 min Qf2 StJ 1'<:: ""N 2d 4 ° H2N~~ o§Q: r "'" \ --= ,\ "N 3 --­ NH2 .. • ~N EIOH, Reflux 4 hr ~:;,..~ ! S OCM. OCC, : /I DMAP : HN"S/lJ ~\ "'- Ib 2b Deprotection _. _. ­----_. ­- -­ -.. 2c 0?2 0H 1'<:: ""N ° Nq eN ° s..J:",s Sd Scheme G.S projected route to get to intermediate eight and nine, as alternative to scheme 3 The modified Scheme G.S to get to ligand Sd by an alternate route proved to be just as difficult. The thiazoline~activatedester is characteristically yellow because of the conjugation of the atoms. The activated thiazoline ester works so well that the diamine 218 that is the backbone for the condensation instead makes an amide bond.37 This characteristic color disappears during the condensation reaction attempts as the diamine reacts with the thiazoline to form an amide. This has proved that the condensation needs to be done before the activation or the capping needs to be done before the condensation. Capping First The second possibility to solve the capping problem is to cap the ligands before they are fully assembled. This alternate scheme will run the same reactions but in a different order. The burgundy line is the spacer, the benzidine (3) or the 4,4"­ diaminotertphenyl (4) that is used in the condensation with the ketone to make the Schiff base. An orange-burgundy-orange line is the same as a blue line from Scheme 3. The orange end is the ketone for the condensation. The R group could be ethyl ester, benzyl ester, acid or the activated thiazoline esters, but here instead the ketone is capped to yield a new intermediate. This new intermediate will undergo self-assembly (using the metals) and condensation (with the diamine core) at the same time. By CAChe modeling, a L3 helicate should be able to form without metal, but because of ligand design the M2L3 complex should not be stable. 219 3 Scheme G.6 Alternate scheme for the capping of the ligands before self-assembly A major concern about condensing the backbone and self-assembling the complex at the same time is that the new intermediate (13) would be a good metal chelator, because it would have the ability to wrap around the metal, much like EDTA.40,41 But CAChe modeling suggests that the Zn center would be strained. Starting with benzyl nicotinate, 1b, and acylation to 2b affords a higher yield than using nicotinic acid, 1c, or ethyl nicotinate, la. Then ketone 2b is modified into ketone 2d; as seen before, 2d cannot be condensed with 3 or 4 to yield ligand 5d or 6d respectively. Therefore 2d will be reacted with TRPN, 9, to yield the capped ketone. This new intermediate will be condensed with a diamine (3 or 4) either in the presence or absence of Zn2+, which should afford the capped metal templated organic nanocage (14) or the non-metal helicate (15). 220 o2o~°oO~ 0 '" ",,,,,«'i~I'" ~ ~N S ~N DC'.'i.occ.D~AP HN.1(o ~s 2bIb IS Scheme G.7 acylation, activation, capping condensation coupled with SA. Future Work Currently we stand two steps from the completion of the first main goal the templated organic nanocage. Those two steps are the capping and then demetallation of the cage. The first objective is to complete the ligand synthesis route and the characterization of the intermediates. Ligands Sa and Sb need to be converted into the acid of Sc, which then must be fully characterized. The same functional group interconversion needs to be finished on the larger ligand 6. Both ligands Sc and 6c will be metallated and the resulting complexes will be characterized. Then free ligands Sc and 6c will be activated into ligands Sd and 6d, which will also be metallated. Each of the ligands (a, b, c or d) should self-assemble into the supramolecular complex. The biggest problem will be the formation of all 12 amide bonds to yield 7 or 8 from Scheme GA. The current progress is showing that we may need to use activated esters to prepare for capping (ligands Sd and 6d). The complexes made with R functional groups a, b or c will still need to be capped after assembly. 221 The final step to yield the organic nanocage is the demetallation of the capped template. The basic plan is to make the metal less stable in the cage and then extract it. Possible demetallation solutions are to reduce the Schiff base to the amine then remove the metal with EDTA7,42,43 or couple a chromatographic separation44 for the easy release of the metal by precipitation of an insoluble metal salt. We will continue working with the existing ligand 5a,b and 6a,b to assemble cages and characterize them. One plan is to use these ligands with other metals centers. Other metals have different coordination geometries. We could exploit this in an attempt to make coordination polymers.45 -47 If coordination polymers are made then they could still be covalently capped and demetallated. They would be very interesting and possibly very useful structures for metal remediation or possibly drug delivery.48 If coordination polymers are not made, instead a discreet species like a square or a grid can be made.49,5o The self-assembly was not accurate because of the DMSO concentration effects (Figure 5). There are a series of experiments to try in DMF, since it appears to allow for the formation of a new discreet species. We will try the same self-assembly reactions with adamantane present, looking for the encapsulation of it as guest during complex formation. Ward noticed that an anionic guest helps with self-assembly their complexes [ref]; we will work more on the self-assembly of tetrahedron Sa using Zn(OTt)2 as the metal source, but determine if the addition of KBF4as a possible guest will accelerate the formation of the complex. The larger cages (8) made from the longer ligand 6, will need a larger anionic guest like 104', Mn04' or Re04·. We will try to self-assemble ligand and 222 complex in one step, using a one-pot synthesis of 2b or 2d, with 3 and Zn(BF4)2 in DMF, or chloroform to see if complex 7b or 7d will form. 51 •52 New Ligands A major branch point is to synthesize different ligands. We plan to build off this existing strategy by using new diarnine spacers. 47.53 Increased size and bulk as well as added flexibility should allow for the synthesis ofM2L3 helicates.54-58 New topologies can also be explored by changing to three- or four-fold symmetric linkers. The new spacers would allow for the formation ofM4L4 cube complexes.59•60 Another aspect of the project would be to work on a new design of ligands that still have a similar binding motif of the Schiff base but are assembled differently and with higher yields. Using a bipyridyl functionality for the binding motif would require alternate functionality on the ends to allow for a linker to make a bis ligand and the covalent cap at the other end. 10.61 Another prime alternative is to use a pyrazolylpyridine binding motif as the bidentate ligand. 18•62 The pyrazolylpyridine rings would be able to be differentially functionalized. Using a catechol adjacent Schiff base would create a new binding motif for the metal. 15 This new binding group could be coupled with any of the current or future diamine cores. These new ligands would be able to achieve different complexes and should also be able to make the coordination polymers.63 This project has many directions that it can go. The existing ligand strategy will yield multiple organic nanocages soon. These cages can then be tested for guest-host chemistry and functionalized for testing with external applications. 223 Experimental General Experimental. All NMR spectra were taken on a 300MHz or a 500MHz Varian lNOVA Spectrometer instrument in CDCI3, unless otherwise noted. All reactions were performed under an inert N2 atmosphere. Compounds were purchased from a commercial supplier and used without further purification unless otherwise noted. ESI­ MS was performed on an Agilent 1100 LC-ESIMS by means of direct injection, using THF as the mobile phase. Desert Analytic of Tucson, AZ performed elemental analysis. Single crystal X-ray data were collected using a Bruker SMART APEX diffractometer equipped with a CCD area detector using Mo-Ka (A = 0.71073 A) radiation. 6-Acetyl.ethyl nicotinic (2a Scheme 3) A chilled solution of H2S04 (5.2 mL, 92 mmol), ethyl nicotinate 1a (4.6 mL, 33 mmol) and acetaldehyde (5.5 mL, 96 mmol, added via a pre-chilled syringe) in water (l5mL) was prepared. A suspension of iron sulfate (26.9 gm, 97 mmol) in water (65 mL) was added drop wise by one syringe while t-butyl peroxide (9.8 mL, 67 mmol, 70% solution in water) was added by a second syringe. Both reagents were added dropwise over three minutes. The reaction was stirred for a total of 15 minutes from the beginning of addition until the removal of the ice bath. The reaction was extracted twice with chloroform (2 x 20 mL). The organic layers were combined and washed once with brine (l x 20 mL), then dried over MgS04, filtered and reduced by rotary evaporation. Crude yield a mixture of la, 2a, 12a and 11a was 3.29 gm, ca. 51.6 %. The product was purified by column chromatography (silica 224 gel, 9:1 hexanes: ethyl acetate). The desired product, 2a, is the first to elute. The other products can be isolated by this method as well. Final yield of 2a was 0.300 gm, 9% of crude. IH NMR b == 9.26 (s, 1H), 8.41 (dd, J == 8.1, 2.7 Hz, 1H), 8.09 (dd, J == 8.1,0.6 Hz, 1H), 4.44 (q, J == 7.0 Hz, 2H), 2.75 (s, 3H), 1.43 (t, J == 7.0 Hz, 3H) Undesired products 1a IH NMR b == 9.22 (s, 1H), 8.76 (dd, J == 4.5, 1.8 Hz, 1H), 8.27 (d oft, J == 6.0, 1.8 Hz, 1H), 7.38 (dd, J == 7.8, 2.7 Hz, 1H), 4.42 (q, J == 7.2 Hz, 2H), 1.30 (t, J == 7.2 Hz, 3H) 11a IH NMR b == 9.19 (s, 1H), 8.22 (d, J == 4.8 Hz, 1H), 7.20 (d, 4J == 0.6 Hz, 1H), 4.41 (q, J == 7.2 Hz, 2H), 2.55 (s, 3H), 1.38 (t, J == 7.2 Hz, 3H) 12a IH NMR b == 9.16 (s, 1H), 7.95 (s, 1H), 4.42 (q, J == 6.9 Hz, 2H), 2.75 (s, 3H), 2.58 (s, 3H), 1.40 (t, J == 6.9 Hz, 3H) 6.Acetyl.benzyl nicotinate. (2b Scheme G.3) A chilled solution of H2S04 (3.4 mL, 58 mmol), benzyl nicotinate, 1b, (5.0 gm, 23 mmol) and acetaldehyde (3.3 mL, 58. mmol, added via a pre-chilled syringe) in water (10 mL) was prepared. A suspension of iron sulfate (16 gm, 58 mmol) in water (20 mL) was added dropwise by one syringe while t­ butyl peroxide (8.0 mL, 58 mmol, 70% solution in water) was added by a second syringe. Both reagents were added dropwise over three minutes. The reaction was stirred for a total of 10 minutes from the beginning of addition until the removal of the ice bath. 225 The reaction was extracted ten times with chloroform (10 x 10 mL). The organic layers were combined and washed once with brine (1 x 20 mL), then dried over MgS04, filtered and reduced by rotary evaporation. The product was purified by column chromatography (silica gel, 9:1 hexanes: ethyl acetate). The desired product, 2b, is the first to elute. The other products can be isolated by this method as well. Final yield of 2b was 1.27 gm, 21.3% yield overall. IH NMR &=9.26 (s, lH), 8.41 (dd, J =8.1, 2.7 Hz, 1H), 8.09 (dd, J =8.1,0.6 Hz, 1H), 7.41 (m, 5H), 5.42 (s, 2H), 2.75 (s, 3H),; l3C NMR & = 164.9, 156.0, 151.2, 150.5, 138.2, 124.2, 121.3,62.1,26.2, 14.5. . CyJa Ion resu Table G 1 A 1 f Its Ester 1a 1a 1a 1a 1a 1b 1b 1b 1b Time (min) 15 15 15 10 10 15 crude % product Product Overall % 57.3 2a 7.5 JTG/MNG 50.9 2a 6.1 JTG/MNG 53.8 2a 7.5 JTG/MNG 73.2 2a 10.1 JTG/MNG 82.2 2a 10.9 JTG/MNG not determined 2b 16.0 CAJ not determined 10 2b 21.3 CAJ not determined 10 2b 17.0 CAJ not determined 10 2b 23.0 MNG/JTG 6·Acetyl.nicotinic Acid, (2c Scheme G.3) (synthesized by CAJ) To a solution of 2b,(0.5 gm, 1.9 mmol) in 3: 1 THF/water two equivalents of KOH was added. The reaction was stirred for three hours without heat. The THF was removed by rotary evaporation and the water was washed with methylene chloride (3 x 10 mL). The organic layers were combined and dried by rotary evaporation to yield un-reacted starting material, 2b. The aqueous layer was acidified with HCl (2 equivalents) to yield a 226 precipitate, which was filtered and washed with water, yielding 0.18 gm ( 47%) of 2c when dried. IH NMR b =8.67 (s, 1H), 8.04 (dd, J =8.1, 1H), 7.73 (dd, J =8.1, 1H), 4.67 (s, 4H), 2.45 (s, 3H) 6-Acetyl-nicotinic Acid Thiazoline Ester, (2d Scheme G.3) (synthesized by CAJ) To a solution of 2c (0. 180gm, 1.08 mmol) in 5 mL methylene chloride and 5 mL tetrahydrofuran, one equivalent of 2-mercaptothizaoline (0.119 gm, 1 mmol) one equivalent of DCC (dicyc1ohexylcarboimide) (0.206 gm, 1 mmol) and one-twentieth equivalent of DMAP (4-(dimethylamino)-pyridine) (0.0061 gm, 0.05 mmol) was added. The reaction was stirred at room temperature under nitrogen for 5 hours, at which point the solution was a deep yellow color. A white precipitate formed and the reaction was filtered to remove the DCD (dicyc1ohexylcarbourea). The crude product was purified by column chromatograph (2: 1 hexanes: ethyl acetate), yield 0.040 gm of yellow solid (thick oil) 2d (15%). IH NMR b =8.85 (s, 1H), 8.03 (s, 2H), 8.09 (dd, J =8.1, 0.6 Hz, 1H), 4.60 (t, J = 6.9 Hz, 2H), 3.52 (t, J = 6.9 Hz, 2H), 2.72 (s, 3H) Schiff Base Ligand. (Sa Scheme G.3) Table 2 entries A-G. To a solution of ketone, 2a, (0.26 gm, 1.3 mmol) in 4 mL of methanol 0.49 equivalents of benzidine 3 (0.124 gm, 0.67 mmol) was added. The reaction was stirred at reflux for four hours. The reaction was then reduced by rotary evaporation and re-suspended in a minimal amount of 9: 1 CHCI3:MeOH solution. Hexanes were then carefully layered on top and crystals formed overnight. The liquid layer was filtered off and the remaining crystals were the desired product Sa. Yield 0.075 gm, 0.14 mmol, 20 %. 227 Schiff Base Ligand. (Sa Scheme G.3) Table 2 entries H-L. To a solution of ketone, 2a, (0.203 gm, 1.05 mmol) in 4 mL of solvent 0.2 equivalents of benzidine 3 (0.038 gm, 0.2 mmol) was added. To the reaction a catalytic amount of acid was added (5 drops of concentrate acid, notes column). The reaction was stirred at reflux for four hours. Within 30 minutes the transparent solution had become opaque with a precipitate. After four hours the reaction was removed from the heat and allowed to cool to room temperature. The reaction was filtered and washed with methanol; the solid was the desired product. Yield 0.095 gm, 0.17 mmol, 85 %. 3 IH NMR 6 = 7.34 (d, J = 8.7 Hz, 4H), 6.73 (d, J = 8.1 Hz, 4H), 3.65 (s, 2H); 13e NMR 6 = 145.3, 127.5, 115.7. Sa IH NMR 6 = 9.26 (s, 2H), 8.36 (s, 4H), 7.64 (d, J = 8.1 Hz, 4H), 6.94 (d, J = 8.4 Hz, 4H), 4.44 (q, J =7.1 Hz, 4H), 2.43 (s, 6H), 1.43 (t, J = 7.1 Hz, 6H); 13e NMR 6 = 166.78, 165.05,159.62, 150.05, 149.80, 137.18, 136.31, 127.25, 126.76, 120.85, 119.73,61.47, 16.52, 14.20, there are fewer than predicted 13e resonances. Based on the purity of 5a according to IH spectra, it is assumed that several 13e resonances have coincidentally identical shifts; ESI-MS rnIz: MH+(calc. 535.23 ,obs. 535.3, 100%), MNa+( calc. 557.22,obs. 557.225%). The crystal was mounted on a quartz fiber with paratone oil. Data in the frames corresponding to an arbitrary hemisphere of data (00 scans, 10 sec frames) were 228 intergrated using SAINT64 [SAINT, SAX Area Detector Intergration Program, Bruker AXS, Inc., Madison, 1995] Data were corrected for Lorentz and polarization effects. The data were further analyzed using XPREp65 [G. M. Sheldrick, SHELXTL, Bruker AXS, Inc., WI, USA, 1997]. An empirical absorption correction based on the measurement of redundant and equivalent reflections and an ellipsoidal model for the absorption surface were applied using SADABS.66 The structure solution and refinement were performed using SHELXTL (refined on F2).67 All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were included but not refined on all appropriate atoms. Crystal size 0.49 x 0.33 x 0.002 mm; T =-120°C; monoclinic, P2/c (#14), a = 27.95 (1) A, b =6.230 (2) A, c =7.747 (3) A, ~ =93.870 (6)0, ; V =1346.0 (8) N, Z =2, Jl =.088 mm,I, F(OOO) =564 Pealed =1.319 g mL,I, 2E>max =52.2720,. Of the 5980 reflections, which were collected, 1909 were unique (Rint = 0.0319); equivalent reflections were merged. Empirical absorption correction: Tmax =0.999, Tmin =0.660. Final R1 = 0.0468 for 1466 data for 1>20(1) (241 Parameters, 0 restraints); for all 1906 data, wR2 = 0.122, GOF = 1.059. Table G.2 - Condensation results for Ligand Sa Reaction Ketone 2a Benzidine 3 solvent time heat notes yield (%) Sa A 2 I Methanol 4 hours Reflux 20 Crude B 2 1 Ethanol 4 hours Reflux 25 Crude C 2 1 Toluene 8 hours Reflux oCrude D 2 I Ethanol 4 hours Reflux 3AMS 25 Crude E 2 1 Ethanol 4 hours Reflux 3A MS, Cat. HCI 10 Crude F 2 1 Ethanol 4 hours Reflux Cat. HCI 45 Crude G 5 1 Ethanol 4 hours Reflux Cat. HCI 65 Crude 229 H 5 1 Ethanol 4 hours Reflux Cat. Acetic 75 Clean I 5 1 Ethanol 4 hours Reflux Cat. Formic 60 Clean J 5 1 MethanollHexanes 8 hours Reflux Cat. Acetic 50 Clean K 5 1 Ethanol 16 hours Reflux Cat. Acetic 85 Clean L 5 1 Ethanol 16 hours Reflux Cat. Acetic 88 Clean Schiff Base Ligand Benzyl ester benzidine core (5b Scheme G.5) To a solution of ketone, 2b, (0.200 gm, 0.783 mmol) in 4 mL of Ethanol 0.2 equivalents of benzidine 3 (0.029 gm, 0.157 mmol) was added. To the reaction a catalytic amount of acetic acid (5 drops) was added. The reaction was allowed to stir at reflux for four hours. Within 30 minutes the transparent solution had become opaque with precipitate. After four hours the reaction was removed from the heat and cooled to room temperature. The reaction was filtered and washed with methanol, the solid was the desired product. Yield 0.054 gm, 0.082 mmol, 52 %. 5b 'H NMR 0 = 9.26 (s, 2H), 8.36 (s, 2H), 8.02 (s, 2H), 7.75 (d, J = 8.4 Hz, 2H), 7.5(m, 5H), 6.94 (d, J = 8.4 Hz, 4H), 5.44 (s, 4H), 2.43 (s, 6H); l3e NMR 0 = 166.82, 165.0, 159.85, 149.95, 149.83, 137.35, 136.41, 135.46, 128.66, 128.26, 127.32, 120.96, 119.77, 115.39,67.14, 16.53; ESI-MS m/z: MH+(calc. 659.27 , obs. Inconclusive) Schiff Base Ligand. (5c Scheme G.3) To a solution of ligand Sa (0.100 gm, 0.187 mmol) in 4 mL of DMSO ,10 equivalents of 1M KOH (2 mL of sol.) was added. The reaction was heated for 16 hours at 95°C, then reduced by rotary evaporation and the product was precipitated with acetone. The reaction was centrifuged and the supernate 230 was decanted and dried down by rotary evaporation. The dried solution was resuspended in minimal 1:1 DMSO:water then precipitated with acetone again. The pellets were combined and washed with excess acetone and then dried. Yield 0.01 gm, 0.01 mmol, 10 %. Schiff Base Ligand Ethyl ester terphenyl core (6a Scheme G.3) To a solution of ketone 2a (0.25 gm, 1.2 mmol) in 4 mL of ethanol, 0.2 equivalents of 4-4"­ terphenyldiamine 4 (0.127 gm, 0.689 mmol) was added. To the reaction a catalytic amount of acetic acid (5 drops) was added. The reaction was stirred at reflux for four hours. Within 30 minutes the transparent solution had become opaque with precipitate. After four hours the reaction was removed from the heat and cooled to room temperature as product precipitated. The reaction was filtered and washed with methanol, then dried, and the solid was the desired product. Yield 0.170 gm, 0.278 mmol, 40 %. IH NMR () = 9.23 (s, 2H), 8.34 (s, 4H), 7.68 (s, 4H), 7.65 (d, J = 7.2 Hz, 4H), 6.91 (d, J = 7.2 Hz, 4H), 4.41 (q, J =7.1 Hz, 4H), 2.41 (s, 6H), 1.40 (t, J = 7.1 Hz, 6H); l3e NMR () = 166.78, 165.05, 159.62, 150.05, 149.80, 137.18, 136.31, 127.25, 126.76, 120.85, 119.73,61.47, 16.52, 14.20 there are fewer than predicted l3e resonances. Based on the purity of 5a according to IH spectra, it is assumed that several l3e resonances have coincidentally identical shifts; ESI-MS m/z: MH+(calc. 611.27 ,obs. 611.2,15%). 4 IH NMR () = 7.34 (d, J = 8.7 Hz, 4H), 6.73 (d, J = 8.1 Hz, 4H), 3.65 (s, 2H) 231 Schiff Base Ligand Benzyl terphenyl core (6b Scheme G.3) To a solution of ketone 2b (0.376 gm, 1.47 mmol) in 4 mL of solvent 0.2 equivalents of 4-4"terphenyldiamine 4 (0.084 gm, 0.323 mmol) was added. To the reaction a catalytic amount of formic acid (5 drops) was added. The reaction was allowed to stir at reflux for four hours. Within 30 minutes the transparent solution had become opaque with precipitate. Mter four hours the reaction was removed from the heat and allowed to cool to room temperature. The reaction was filtered and washed with methanol and hexanes through a plug of silica gel. Yield 0.15 gm, 63 %. IH NMR () = 9.26 (s, 2H), 8.36 (s, 4H), 7.70 (s, 4H), 7.67 (d, J = 8.1 Hz, 4H), 6.93 (d, J = 8.4 Hz, 4H), 4.44 (q, J =7.1 Hz, 4H), 2.43 (s, 6H), 1.43 (t, J = 7.1 Hz, 6H); 13C NMR () = 166.78, 165.05, 159.62, 150.05 149.80, 138.2 137.18, 136.31, 127.6, 127.25, 126.76, 120.85, 119.73,61.47, 16.52, 14.20, there are fewer than predicted 13C resonances. Based on the purity of 5a according to IH spectra, it is assumed that several 13C resonances have coincidentally identical shifts; ESI-MS m/z: MH/+ (calc. 368.15, obs. 368.2, 100%), MH+( calc. 735.3, obs. 735.4 10%). Schiff Base Ligand. (6c Scheme G.3) To a solution of ligand, 6b, (0.6 gm, 2 mmol) in 3: 1 THF/water two equivalents of KOH was added. The reaction was stirred for five hours without heat. The THF was removed by rotary evaporation and the water was washed (3 x 10 mL) with DCM. Organic layers combined and dried down to yield un­ reacted starting material, 6b. The aqueous layer was acidified with HCI (2 equivalents) to yield a precipitate, the solid was filtered and washed with water, yielding 0.141 gm ( 23.5%) of 6c when dried. Carried on to 6d without characterization. 232 Schiff Base Ligand. (6d Scheme G.3) To a solution of ligand, 6c (0.180 gm, 1.08 mmol) in 5 mL DCM and 5 mL THF, one equivalent of 2-mercaptothiazoline (0.119 gm, 1.08 mmol) one equivalent of EDCI (0.192 gm, 1 mmol) and one twentieth equivalent of DMAP (6.2 gm, 0.05 mmol) was added. The reaction was stirred at room temperature under nitrogen for 5 hours, at which point the solution was a deep yellow color. A white precipitate formed, the reaction was filtered to remove the EDUI. The crude product was purified by column chromatograph (2:1 hexanes: Ethyl acetate). Yields 0.05 gm of yellow solid (thick oil) 6d (28%). Characterization is currently being done. 233 BIBLIOGRAPHY Chapter I 1. Johansson, G., Acta Chern. Scand 1960,14,771-773. 2. Anderson, 1. S., Constitution of the Poly-acids. Nature 1937, 140,850. 3. Casey, W. H., Large Aqueous Aluminum Hydroxide Molecules. Chern. Rev. 2006, 106, 1. 4. Pope, M. T., Heteropoly and isopoy Oxornetalates. 1983. 5. Lorenzo-Luis, P. A; GHi, P., Polyoxometalates with an Anderson-Evans structure. Recent Res. Devel. Inorg. Chern. 2000, 2, 185-196. 6. Long, D.-L.; Burkholder, E.; Cronin, L., Polyoxometalate clusters, nanostructures and materials: From self-assembly to designer materials and devices. Chern. Soc. Rev. 2007, 36, 105. 7. Jeannin, Y. P., The Nomenclature ofPolyoxometalates: How To Connect a Name and a Structure. Chern. Rev. 1998, 98, 51. 8. Gouzerh, P.; Proust, A., Main-Group Element, Organic, and Organometallic Derivatives ofPolyoxometalates. Chern. Rev. 1998,98, 77. 9. Weinstock, 1. A, Homogeneous-Phase Electron-Transfer Reactions of Polyoxometalates. Chern. Rev. 1998,98, 113. 10. Kozhevnikov,1. V., Catalysis by Heteropoly Acids and Multicomponent Polyoxometalates in Liquid-Phase Reactions. Chern. Rev. 1998, 98, 171. 11. Sadakane, M.; Steckhan, E., Electrochemical Properties ofPolyoxometalates as Electrocatalysts. Chern. Rev. 1998,98,219. 12. MUller, A; Peters, F.; Pope, M. T.; Gatteschi, D., Polyoxometalates: Very Large ClusterssNanoscale Magnets. Chern. Rev. 1998,98,239. 13. Klemperer, W. G.; Wall, C. G., Polyoxoanion Chemistry Moves toward the Future: From Solids and Solutions to Surfaces. Chern. Rev. 1998, 98, 297. 234 14. Yamase, T., Photo- and Electrochromism ofPolyoxometalates and Related Materials. Chern. Rev. 1998, 98, 307. 15. Rhule, J. T.; Hill, C. L.; Judd, D. A; Schinazi, R. F., Polyoxometalates in Medicine. Chern. Rev. 1998, 98, 327. 16. Katsoulis, D. E., A Survey of Applications ofPolyoxometalates. Chern. Rev. 1998,98, 359. 17. Cronin, L.; Beugholt, c.; Krickermeyer, E.; Schmidtamann, M.; Bagge, H.; Kogerler, P.; Luong, T. K. K.; Muller, A, "Molecular Symmetry Breakers" Generating Metal-Oxide-Based Nanoobject Fragments as Synthons for Complex Structures: [{Mo128E140388HlO(H20)81 hho , a Giant-Cluster Dimer. Angew. Chern. Int. Ed 2002,41,2805. 18. Muller, A; Krickermeyer, E.; Bagge, H.; Schmidtamann, M.; Peters, F., Organizational Forms ofMatter: An Inorganic Super Fullerene and Keplerate Based on Molybdenum Oxide. Angew. Chern. Int. Ed 1988,37,3359. 19. Muller, A; Beckmann, E.; Bagge, H.; Schmidtamann, M.; Dress, A, Inorganic Chemistry Goes Protein Size: A M0368 Nano-Hedgehog Initiating Nanochemistry by Symmetry Breaking. Angew. Chern. Int. Ed 2002,41, 1162. 20. Muller, A.; Beugholt, C.; Bagge, H.; Schmidtamann, M., Influencing the Size of Giant Rings by Manipulating Their Curvatures: N~[Mo1200366(H20)48H12{Pr(H20)5}6]·(200H20) with Open Shell Metal Centers at the Cluster Surface. Inorg. Chern. 2000, 39, 3112. 21. Muller, A; Serain, c., Soluble Molybdenum Blues- "des Pudels Kern". Ace. Chern. Res. 2000, 33, 2. 22. Muller, A.; Shan, S. Q. N.; Bagge, H.; Schmidtamann, M.; Kogerler, P.; Hauptfleisch, B.; Leiding, S.; Wittler, K., Thritry Electrons "trapped" in a Sperical Matrix: A Molybdenum Oxide-Based Nanostructured Keplerate Reduced by 36 Electrons. Angew. Chern. Int. Ed 2000,39, 1614. 23. Honda, D.; Ikegami, S.; Inoue, T.; Ozeki, T.; Yagasaki, A, Protonation and Methylation of an Anderson-Type Polyoxoanion [IM06024t. inorg. Chern. 2007, 46,1464. 24. Murugesu, M.; Clerac, R.; Wernsdorfer, W.; Anaon, C. E.; Powell, A K., Hierarchical Assembly of {FeB} Oxygen-Bridged Clusters into a Close-Packed Superstructure. Angew. Chern. Int. Ed 2005,44, 6678. 235 25. Goodwin, J. c.; Sessoli, R.; Gatteschi, D.; Wernsdorfer, W.; Powell, A. K.; Heath, S. L., Towards nanostcutred Arrays of Single Molecular Magnets: new Fel9 oxyhydroxide clusterd displaying high ground state spins and hysteresis. J. Chem. Soc. Dalton Trans. 2000, 1835. 26. Pohl, 1. A. M.; Westin, L. G.; Kritikos, M., Preparation, Structure, and Properties ofa New Giant Manganese Oxo-Alkoxide Wheel, [MnI9012(OC2H40CH3)14(HOC2H40CH3)1O]·HOC2H40CH3. Chem. - Eur. J. 2001,7,3439. 27. Evans, H. T., Jr, The Molecular Structure of the Hexamolybdotellurate Ion in the Crystal Complex with Telluric Acid, (NI-4)6ITeM060Zl]. Te(OH)6.7H20. Acta Cryst. 1974, B30, 2095. 28. Nordin, J. P.; Sullivan, D. 1.; Phillips, B. L.; Casey, W. H., Mechanism for fluoride-promoted dissoultion ofbayerite [B-Al(OH3)(s)] and boehmite [g­ AlOOH]: 19F -NMR Spectroscopy and aqueous Surface Chemistry. Geochimica et Cosmochimica Acta 1999, 63, (21), 3513. 29. Johansson, G., The Crystal Strucutres of [Ah(0H)2(H20)S](S04)2 • 2H20 and [Ah(OHMH20)s](Se04)2 • 2H20. Acta Chem. Scand 1962, 16,403. 30. Casey, W. H.; Phillips, B. L., Kinetics of oxygen exchange between sites in the Ga04AL2(OH)24(H20)12 7+(aq) molecule and aqueous solution. Geochimica et Cosmochimica Acta 2001,65, (5), 705. 31. Filowitz, M.; Ho, R. K. c.; Klemperer, W. G.; Shum, W., 170 Nuclear Magnetic Resonance Spectroscopy of Polyoxometalates. 1. Sensitivity and Resolution. Inorg. Chem. 1979, 18, 93. 32. Kortz, u.; Jeannin, Y. P.; Teze, A.; Herve, G.; Isber, S., A Novel Dimeric Ni­ Substituted beta-Keggin Silicotungstate: Structure and Magnetic Properties of Kn[ {(3-SiNhWI0036(OHh(H20)h]·20H20. Inorg. Chem. 1999, 38, 3670. 33. Teze, A.; Cadot, E.; Bereau, V.; Herve, G., About the Keggin Isomers: Crystal Structure of [N(C4H91,4kgamma-[SiW1204o], the gamma-Isomer ofthe Keggin Ion. Synthesis and IS W NMR Characterization of the Mixed gamma­ [SiM02WI004o]n-(n = 4 or 6). Inorg. Chem. 2001,40,2000. 34. Rowsell, 1.; Nazar, L. F., Speciation and Thermal Transformation in Alumina Sols: Structures of the Polyhydroxoa1uminum Cluster [AhoOs(OH)56(H20h6]IS+ and its 8-Keggin Moiete. J. Am. Chem. Soc. 2000, 122,3777-3778. 236 35. Son, J.-H.; Kwon, Y.-D., Crystal Engineering through Face Interactions between Tetrahedral and Octahedral Building Blocks: Crystal Structure of [E­ Al1304(OH)24(H20)12h[V2W4019]3(OH)2·27H20. Inorg. Chern. 2004,43, 1929. 36. Allouche, L.; Gerardin, C.; Loiseau, T.; Ferey, G.; Taulelle, F., Aho : Giant Aluminum Polycation. Angew. Chern. Int. Ed 2000, 39, 511-514. 37. Xin, F.; Pope, M. T.; Long, G. J.; Russo, U., Polyoxometalate Derivatives with Multiple Organic Groups. 2. Synthesis and Structures of Tris(organotin) a, b­ Keggin Tungstosilicates. Inorg. Chern. 1996,35, 1207. 38. Evans, H. T., Jr, The Crystal Structures of Ammoium and Potassium Molydotellurates. J. Arn. Chern. Soc. 1948, 70, (3), 1291. 39. Heath, S. L.; Jordan, P. A; Johnson, I. D.; Moore, G. R.; Powell, A. K.; Helliwell, M., Comparative X-ray and 27Al NMR Spectroscopic Studies of the Speciation of Aluminum in Aqueous Systems: Al(III) Complexes of N(CH2C02H)2(CH2CH20H). J. Inorg. Biochern. 1995,59, 785-794. 40. Seichter, W.; Mogel, H.-J.; Brand, P.; Salah, D., Crystal Structure and Formation of the Aluminum Hydroxide Cloride [Al13(OHh4(H20h4]Chs • 13 H20. Eur. J. Inorg. Chern. 1998, 795-797. 41. Rather, E.; Gatlin, J. T.; Nixon, P. G.; Tsukamoto, T.; Kravtsov, V.; Johnson, D. W., A Simple Organic Reaction Mediates the Crystallization of the Inorganic Nanocluster [Ga13(""3-0H)6(""2-0H)18(H20)24](N03)lS. J. Arn. Chern. Soc. 2005, 127, 3242-3243. 42. Goodwin, J. c.; Teat, S. J.; Heath, S. L., How do clusters grow? The Synthesis and Structure of Polynuclear Hydroxide Gallium(III) Clusters. Angew. Chern. Int. Ed 2004,43,4037-4041. 43. Rujiwatra, A; Mander, G. J.; Kepert, C. J.; Rosseinsky, M. J., Cryst. Growth Des. 2005, 5, 183. 44. Casey, W. H.; Olmstead, M. M.; Phillips, B. L., A New Aluminum Hydroxide Octamer, [A18(OH)14(H20)18](S04)5·16H20. Inorg. Chern. 2005,44,4888. 45. Takada, K.; Onoda, M.; Argyriou, D. N.; Choi, Y.-N.; Izumi, F.; Sakurai, H.; Takayama-Muroachi, E.; Sasaki, T., Order and Disorder Aspects ofInterlayer guests in Superconducting Hydrous Sodium Cobalt Oxides. Chern. Mater. 2007, 19, (14), 3519. 237 46. Wery, A. S. J.; Gutierrez-Zorrilla, J. M.; Luque, A.; Ugalde, M.; Roman, P.; Lezama, L.; Rojo, T., Synthesis, Crystal Structure, and Vibrational and Electron Spin Resonance Study oftert-Butylammonium [H9-nCrM06024J ·mH20 (n=2, m=2; n=3, m=8). Effects of Degress fo Protonation and Hydration. Acta Chem. Scand 1998,52,1194. 47. Orpen, G. A.; Brammer, L.; Allen, F. H.; Kennard, 0.; Watson, D. G.; Taylor, R, Tables of Bond Lengths Determined by X-Ray and Neutron Diffraction 2. Organometallic Compouns and Coordination complexes of the D-Block and F­ Block Metals. J. Chem. Soc. Dalton Trans. 1989, Sl. 48. Shannon, R. D., Revised Effective Ionic Radii and Systematic Studies of Interatomie Distances in Halides and Chaleogenides. Acta Cryst. 1976, A32, 751. 49. CSD 2006, Cambridge Cryastallographic Data Centre. 50. Hasenknopf, B.; Delmont, R; Herson, P.; Gouzerh, P., Anderson-Type Heteroplymolybdates Containing Tris(alkoxo) Ligands: Synthesis adn Structure Characterization. Eur. J. Inorg. Chem. 2002, 1081. 51. Khan, M. 1.; Tabussum, S.; Doedens, R J.; Golub, V. 0.; O'Connor, C. J., Synthesis, structure and magnetic properties of a novel ferromagnetic cluster [FeV60d(OCH2CH2hN(CH2CH20H)hJCh.lnorg. Chem. Commun. 2004,7,54. 52. Khan, M. 1.; Tabussum, S.; Doedens, R J.; Golub, V. 0.; O'Connor, C. J., Functionalized Metal Oxide Clusters: Synthesis, Characterization, Crystal Structures, and Magnetic Properties of a Novel Series of Fully Reduced Heteropolyoxovanadium Cationic Clusters Decorated with Organic Ligandss[MVIV 606 {(OCH2CH2)2N(CH2CH20H)hJX (M) Li, X) Cl·LiCl; M) Na, X) Cl·H20; M) Mg, X) 2Br·H20; M) Mn, Fe, X) 2Cl; M) Co, Ni, X ) 2CHiH20). Inorg. Chem. 2004,43, 5850. 53. Favette, S.; Hasenknopf, B.; Vaissermann, J.; Gouzerh, P.; Roux, C., Assebly of a polyoxometalate into an anisotropic getl. Chem. Commun. 2003,2664. 54. Kurata, T.; Hayashi, Y.; Uehara, A.; Isobe, K, Synthesis of a reduced Tridecavanadate Dimer Linked by eight Hydrogen Bonds. Chem. Letters 2003, 32, (11), 1040. 55. An, H.; Guo, Y.; Li, Y.; Wang, E.; Lti, J.; Xu, L.; Hu, C., A novel organic­ inorganic hybrid with Anderson type polyanions as building blocks: [(G1Y)2Cu] [Na(H20)4Cr(OH)6M0601sJ 9.5H20 (Gly=glycine). Inorg. Chem. Commun. 2004,7,521. 238 56. An, H.; Li, Y.; Wang, E.; Xiao, D.; Sun, C.; Xu, L., Self-Assembly ofa Series of Extended Architectures Based on Polyoxometalate Clusters and Silver Coordination Complexes. Inorg. Chem. 2005, 44, 6062. 57. He, Q.; Wang, E., Hydrothermal synthesis and crystal structure ofa new molybdenum(VI) areseate(lII), Co"\en)3H30[(CO"06)Mo6vIOlS(As/"03h]e2H20.Inorg. Chem. Acta 1999, 295, 244. 58. Chen, Y.; Zhu, H.; Liu, Q.; Chen, c., Sodium Triethanolamine Complex with Extended 3-D Network Structure. Chem. Letters 1999, 585. 59. Chen, Y.; Liu, Q.; Deng, Y.; Zhu, H.; Chen, C.; Fan, H.; Liao, D.; Gao, E., Vanadium, Molybdenum, and Sodium Triethanolamine Complexes Derived from a Assembly System Containing Tetrathiometalate and Triethanolamine. Inorg. Chem. 2001, 40, 3725. 60. Zhang, Q.-Z.; Yu, Y.-Q.; Chen, S.-M.; He, X; Yan, Y.; Liu, J.-H.; Chen, L.-l; Xia, C.-K.; Xu, X-J.; Wu, X-Y.; Lu, C.-Z., ChineseJ. Struct. Chem. 2004,23, 1269. 61. He, Q.; Wang, E., Hydrothermal synthesis and crystal structure ofa new copper(II) molybdenum(IV) areseate(III), C(csHsNH)2(H30)2[(CO,,06)Mo6VIOlS(As3III03h].Inorg. Chem. Commun. 1999,399. 62. Cui, Y.; Chen, l-T.; Huang, l-S., Syntheses, Crystals structures and magnetic properties of Heterometallic copper-lanthanide clusters [CU12Ln6(Jl3-0H)24(Jl­ 02CR)dH20)lS(Jl12-C104)]s+ (Ln = La, Nd; R = CH2Cl, CCb). Inorg. Chem. Acta 1999, 293, 129. 63. Shivaiah, V.; Nagaraju, M.; Das, S. K., Formation of a Spiral-Shaped Inorganic­ Organic Hybrid Chain, [Cu"(2,2'-bipy)(H20)2A1(OH)6Mo601s]n n-: Influence of Intra- and Interchain Supramolecular Interactions. Inorg. Chem. 2003, 42, 6604. 64. Affronte, M.; Cornia, A; Lascialfari, A; Borsa, F.; Gatteschi, D.; Hinderer, J.; Horvatic, M.; Jansen, A G. M.; Julien, M.-H., Observation ofMagnetic Level Repulsion in Fe6:Li Molecular Antiferromagnetic Rings. Phys. Rev. Lett. 2002, 88, (16), 167201. 239 65. An, H.; Lan, Y.; Li, Y.; Wang, E.; Hao, N.; Xiao, D.; Duan, L.; Xu, L., novel chain-like polymer constructed from heteropolyanions covalently linked by lanthanide cations: (CSH9N02l2[La(H20)7CrM06H6024] • IIH20(Proline=CsH9N02).Inorg. Chern. Cornrnun. 2004,7,356. 66. Li, F.; Xu, L.; Wei, Y.; Wang, X; Wang, W.; Wang, E., Arsenicum-centered Molybdenum-Vanadium polyoxometalates bearing transition metal complexes: Hydrothermal syntheses, crystal structures and magnetic properties. J. Mol. Struct. 2005,753,61. 67. Janas, Z.; Jerzykiewicz, L. B.; Sobota, P.; Dtko, J., Synthesis and crystal structures of the heptamagnesium cationic and mixed magnesium(II)/nickel(II) molecular 2-tetrahydrofurfuroxo aggregates. New J. Chern. 1999, 23, 185. 68. Ochsenbein, S. T.; Murrie, M.; Rusanov, E.; Stoeckli-Evans, H.; Sekine, c.; Glidel, H. D., Synthesis, Structure, and Magnetic Properties of the Single- Molecule Magnet [Ni21 (cit)n(OH)1O(H20)lO] 16-. Inorg. Chern. 2002,41, 5133. 69. Kaziev, G. Z.; Dutov, A A; Quinones, S. H.; Belsky, V. K; Stash, A 1.; A, 1., Russ. Coord Chern. 2004,30,83. 70. Ouahab, L.; Golhen, S.; Yoshida, Y.; Saito, G., J. Cluster Sci. 2003, 14, 193. 71. Jones, L. F.; Brechin, E. K; Collison, D.; Raftery, J.; Teat, S. l, New Routes to High Nuc1eartiy Clusters: Flouride-Based Octametallic and Tridecametallic Clusters of Manganese. Inorg. Chern. 2003,42,6971. 72. Harden, N. C.; Bolcar, M. A; Wemsdorfer, W.; Abboud, K A; Streib, W. E.; Christou, G., Heptanuc1ear and Decanuc1ear Manganese Complexes with the Anion of2-Hydroxymethylpyridine. Inorg. Chern. 2003,42, 7067. 73. An, H.; Xiao, D.; Wang, E.; Li, Y.; Xu, L., A series of new polyoxoanion-based inorganic-organic hybrids: (C6N02Hs)[(H20 MC6N02Hs)Ln(CrM06H60 24)] ·4H20 (Ln = Ce, Pr, La and Nd) with a chirallayer structure. New J. Chern. 2005, 29,667. 74. Goe1, S. c.; Matchett, M. A; Chiang, M. Y.; Buhro, W. E., A Very large Calcium Dialkoxide Molecular Aggregate haveing a CdI2 Core Geometry: Ca9(OCH2CH20Me)18(HOCH2CH20Me)2. J. Arn. Chern. Soc. 1991, 113, 1844. 75. Boulmaaz, S.; Papiemik, R.; Hubert-Pfalzgraf, L. G.; Vaissermann, l; Daran, l­ C., Synthesis and molecular structure ofCd9(OC2~OMe)18,2HOC2H40Me, the fIrst cadmium aggregate based on oxygen donor ligands. Polyhedron 1992, 11, (11),1331. 240 76. Kahn, M. 1.; Chang, y.; Chen, Q.; Hope, H.; Parking, S.; Goshorn, D. P.; Zubieta, J., (Organoaronato)polyoxovandaium Clusters: Properties and Structures of the V(v) clusters. Angew. Chern. Int. Ed 1992,31, (9), 1197. 77. Shivaiah, V.; Das, S. K., Polyoxometalate-Supported Transition Metal Complexes and Their Charge Complementarity: Synthesis and Characterization of [M(OH)6Mo6018 {Cu(Phen)(H20)2} £1 [M(OH)6Mo6018 {Cu(Phen)(H20) Cl}z]-5H20 (M) A13+, Cr3+). Inorg. Chern. 2005,44,8846. 78. Abbati, G. L.; Cornia, A; Fabretti, A c.; Malavasi, W.; Schenetti, L.; Caneschi, A.; Gatteschi, D., Modulated Magnetic Coupling in Alkoxoiron(III) Rings by Host-Guest Interactions with Alkali Metal Cations. inorg. Chern. 1997, 36, 6443. 79. Saalfrank, R W.; Bernt, 1.; Uler, E.; Hampel, F., Template-Mediated Self Assembly of Six- and Eight-Member Iron Coronates. Angew. Chern. Int. Ed 1997, 36, 2428. 80. Bolcar, M. A; Aubin, S. M. 1.; Folting, K.; Hendrickson, D. N.; Christou, G., A new Manganese Cluster topology capable ofyielding high spin species: mixed­ valence [Mn7(OH)3Cb(hmp)9f+ with S 2: 10. Chern. Cornrnun. 1997, 1485. 81. Abbati, G. L.; Cornia, A; Fabretti, A C.; Caneschi, A; Gatteschi, D., A Ferromagnetic Ring of Six Manganese(III) Ions with a S = 12 Ground State. Inorg. Chern. 1998,37, 1430. 82. Golhen, S.; Ouahab, L.; Grandjean, D.; Molinie, P., Preparation, Crystal Structures, and Magnetic and ESR Properties of Molecular Assemmblies of Ferrocenium Derivatives and Paramagnetic Polyoxometalates. Inorg. Chern. 1998, 37, 1499. 83. Saalfrank, R W.; Prakash, R; Maid, H.; Hampel, F.; Heinemann, F. W.; Trautwein, A X.; Bottger, L. H., Synthesis and Characterization ofMetal­ Centered, Six-Membered, Mixed-Valent, Heterometallic Wheels of Iron, Manganese, and Indium. Chern. - Eur. J. 2006, 12,2428. 84. Marcoux, P. R; Hasenknopf, B.; Vaissermann, J.; Gouzerh, P., Developing Remote Metal Binding Sites in Heteropolymolybdates. Eur. J. Inorg. Chern. 2003, 2406. 85. Zhang, J.-1.; Sheng, T.-L.; Xia, S.-Q.; Leibeling, G.; Meyer, F.; Hu, S.-M.; Fu, R.­ B.; Xiang, S.-C.; Wu, x.-t., Syntheses and Characterizations of a Series of Novel Ln6Cu24 Clusters with Amino Acids as Ligands. Inorg. Chern. 2004,43,5472. 241 86. Saalfrank, R. W.; Nakajima, T.; Mooren, N.; Scheurer, A; Maid, H.; Hampel, F.; Trieflinger, C.; Daub, J., Syntheses and Properties of Metal-Centered Mixed­ Valent [NEtt] {Mn" [Mn"3MnIII 3C16(L)6]} Manganese Wheels. Eur. J. Inorg. Chern. 2005, 1149. 87. Abbati, G. L.; Cornia, A; Fabretti, A. C; Caneschi, A; Gatteschi, D., Structure and Magnetic Properties of a Mixed-Valence Heptanuclear Manganese Cluster. Inorg. Chern. 1998,37, 3759. 88. Brechin, E. K; Clegg, W.; Murrie, M.; Parsons, S.; Teat, S. J.; Winpenny, R. E. P., Nanoscale Cages of Manganese and Nickel with "Rock Salt" Cores. J. Arn. Chern. Soc. 1998, 120, 7365. 89. Hayashi, Y.; Fukuyama, K; Takatera, T.; Uehara, A, Synthesis and Structure ofa New Reduced Isopolyvanadate, [V17042]4-. Chern. Letters 2000, 770. 90. Abbati, G. L.; BruneI, L.-C.; Casalta, H.; Cornia, A; Fabretti, A c.; Gatteschi, D.; Hassaon, A K; Jansen, A G. M.; Maniero, A L.; Pardi, L.; Paulsen, C.; Segre, U., Single-Iron versus Dipolar Origin of the Magnetic Anisotropy in Iron(III)-oxo Clusters: A Case Study. Chern. - Eur. J. 2001, 7, 1796. 91. An, H.; Xiao, D.; Wang, E.; Sun, C.; Xu, L., Organic-inorganic hybrids with three-dimensional supramo1ecular channels based on Anderson type polyoxoanions. J. Mol. Struct. 2005, 743, 117. 92. Koizumi, S.; Nihei, M.; Nakano, M.; Oshio, H., Antiferromagnetic Fe(III)6 Ring and Sinle-Mo1ecule Magnet Mn(II)3Mn(III)4 Wheel. Inorg. Chern. 2005,44, 1208. 93. Liu, C.-M.; Huang, Y.-H.; Zhang, D.-Q.; Gao, S.; Jiang, F.-C.; Zhang, J.-Y.; Zhu, D.-B., Cryst. Growth Des. 2005, 5, 1531. 94. Caneschi, A; Cornia, A; Fabretti, A C.; Foner, S.; Gatteschi, D.; Grandi, R.; Schenetti, L., Synthesis, Crystal Structure, Magnetism, and Magnetic Anisotropy of Cyclic Clusters Comprising Six Iron(III) Ions and Entapping Alkaline Ions. Chern. - Eur. J. 1996,2, 1379. 95. Sun, Z.; Gantzel, P. K.; Hendrickson, D. N., Supercubane Mixed-Valence Tridecanuclear Manganese Complex. Inorg. Chern. 1996, 35, 6640. 96. Tesmer, M.; Muller, B.; Vahrenkamp, H., Oligonuclear zinc complexes of2­ pyridylmethanol. Chern. Cornrnun. 1997, 721. 242 97. Oshio, H.; Hoshino, N.; Ito, T.; Nakano, M.; Renz, F.; Glitlich, P., Hihg-Sping Whell of Heptanuclear Mixed Valent Fe(ii,iii) Complex. Angew. Chern. Int. Ed 2003, 42, (2), 223. 98. Schmitt, W.; Baissa, E.; Mandel, A; Anson, C. E.; Powell, A K, [Ahs(J.l3­ O)4(1l3-0HMIl-OH)14(hpdta)3t - A New Ahs Aggergate Which forms a Suprmolecular Zeotype. Angew. Chern. Int. Ed 2001,40,3578-3581. 99. Mehring, M.; Mansfe1d, D.; Sanna, P.; Schiirmann, M., Polynuclear Bismuth-Oxo Clusters: Insight into the Formation Process of a Metal Oxide. Chern. - Eur. J. 2006, 12, 1767. 100. Lee, D.; Jang, S.-J.; Joo, H.-C.; Park, K-M., Triguanidinium hexahydrogenhexa­ molybdocobaltate(III) tetrahydrate. Acta Cryst. 2003, E59, m345. 101. An, H.; Xiao, D.; Wang, E.; Sun, C.; Li, Y.; Xu, L., Synthesis and characterization of two new extended structures based on Anderson-type polyoxoanions. J. Mol. Struct. 2005,751, 184. 102. Duan, L.-M.; Xu, l-Q.; Xie, F.-T.; Cui, X-B.; Ding, H.; Song, l-F., Mendeleev Cornrnun. 2005,79. 103. Labat, G.; Boskovic, c.; Glidel, H. D., Hexakis(l4-2-amino-2-methylpropane-1,3­ dio1ato)hexach10roheptairon(II,III) acetonitrile diso1vate monohydrateq. Acta Cryst. 2005, E61, m611. 104. Murrie, M.; Stoeck1i-Evans, H.; Glidel, H. D., Assembly ofNh and NhJ Molecular Clusters by using Citric Acid. Angew. Chern. Int. Ed 2001, 40, (l0), 1957. 105. Khan, M. I.; Tabussum, S.; Doedens, R. J., A novel cationic heteropolyoxovanadium(IV) cluster functiona1ized with organic ligands: synthesis and characterization of the fully reduced species [MnIIVIV606{(OCH2CH2)2N(CH2CH20H)}6]C12. Chern. Cornrnun. 2003, 532. 106. Lee, D.; Jang, S.-l; Joo, H.-C.; Park, K-M., Anhydrous octaguanidinium hexatungstop1atinate(IV). Acta Cryst. 2003, E59, ml16. 107. An, H.; Xiao, D.; Wang, E.; Li, Y.; Wang, X; Xu, L., Open-Framework Polar Compounds: Synthesis and Characterization of Rare-Earth Po1yoxometa1ates (C6N02HsMLn(H20)s(CrM06H6024)}0.5H20 (Ln = Ce and La). Eur. J. Inorg. Chern. 2005, 854. 243 108. Murugesu, M.; Habrych, M.; Wernsdorfer, W.; Abboud, K. A.; Christou, G., Single-Molecul Magnets: Mn25 Complex with a record S = 51/2 sping for a Molecular Species. J. Arn. Chern. Soc. 2004, 126,4766. 109. Morosin, B., Molecular Configuration of Tridecazirconium oxide-methoxide complexes. Acta. Cryst. Sect. B 1977, 33, 303. 110. Heath, S. L.; Powell, A. K., The Trapping ofIron Hydroxide Units by the Ligand "HEIDI"; Two new Hydroxo(oxo)iron Clusters Containing 19 and 17 Iron Atoms. Angew. Chern. Int. Ed 1992,31, 191. 111. Morgenstern, B.; Sander, 1.; Huch, V.; Hegetschweiler, Complexation of a Hetapnuc1ear Polyoxotantalate Anion with K+: Formation of a Supramolecular [.Kt;-(",,-OH2k(OH2)8]6+ Ring Structure. Inorg. Chern. 2001,40,5307. 112. Brockman, 1. T.; Huffman, J. C.; Christou, G., A High Nuc1earity, Mixed-Valence Manganeses (III,IV) Complex: [Mn21024(OMe)g(02CCH2tBu)16(H20)1O]. Angew. Chern. Int. Ed 2002,41,2506. 113. Zaleski, C. M.; Depperman, E. C.; Denrinou-Samara, C.; Alexiou, M.; Kampf, 1. W.; Kessissoglou, D. P.; Kirk, M. L.; Pecoraro, V. L., Metallacryptate Single­ Molecule Magnets: Effect ofLower Molecular Symmetry on Blocking Temperature. J. Arn. Chern. Soc. 2005, 127, 12862. 114. Day, V. W.; Klemperer, W. G.; Pafford, M. m., Methyltriskaidecazirconates, Molecular froms of Zirconia. Inorg. Chern. 2005, 44, 5397. 115. Denrinou-Samara, C.; Alexiou, M.; Zaleski, C. M.; Kampf, 1. W.; Kirk, M. L.; Kessissoglou, D. P.; Pecoraro, V. L., Synthesis and Magnetic Properties ofa Metallcryptate that behaves as a Single-Molecular Magnet. Angew. Chern. Int. Ed 2003,42, 3763. 116. Smith-Jones, P. M.; Stolz, B.; Bruns, C.; Albert, R.; Reist, H. W.; Freidrich, R.; Macke, H. R., Gallium-67/Gallium-68-[DFO]-Octreotide-A Potential Radiopharmaceutical for PET Imaging of Somatostatin Receptor-Positive Tumors: Synthesis and Radiolabeling In Vitro and Preliminary In Vivo Studies. J. Nuc. Med 1994,35, (2), 317. 117. Hoffend, 1.; Mier, W.; Schuhmacher, 1.; Schmidt, K.; Dimitrakopoulou-Strauss, A.; Strauss, L. G.; Elsehut, M.; Kinscherf, R.; Haberkorn, U., Gallium-68-DOTA­ albumin as a PET blood-pool marker: experimental evaluation in vivo. Nuc. Med Bio. 2005,32, (3), 287. 244 118. Kersting, B.; M. Meyer; Powers, R. E.; Raymond, K. N., Dinuclear Catecholate Helicates: Their Inversion Mechanism. J. Arn. Chern. Soc. 1996, 118, 7221. 119. Cohen, S. M.; Raymond, K. N., Catecholate/salicylate heteropodands: Demonstration of a catecholate to salicylate coordination change. Inorganic Chernistry 2000, 39, (16), 3624-3631. 120. Johnson, D. W.; Raymond, K. N., The Self-Assembly of a G~L6 Tetrahedral Cluster Thermodynamically Driven by Host-Guest Interactions. Inorg. Chern. 2001,40,5157-5161. 121. Gatlin, 1. T.; Mensinger, Z. L.; Meyers, S. T.; Zakharov, L. N.; Keszler, D. A; MacInnes, D.; Johnson, D. W., Heterometallic Group 13 Keggin-like Nanoclsuters. Manuscript in preparation. 122. Gerasko, O. A; Mainicheva, E. A; Naumov, D. Y.; Kuratieva, N. V.; Sokolov, M. N.; Fedin, V. P., Synthesis and Crystal Structure of Unprecedented Oxo/Hydroxo-Bridged Polynuclear Gallium(I1I) Aqua Complexes. Inorg. Chern. 2005,44,4133. 123. Mainicheva, E. A; Gerasko, O. A; She1udyakova, L. A; Naumov, D. Y.; Naumova, M. I.; Fedin, V. P., Synthesis and crystal structures ofsupramolecular compounds of polynuclear aluminum(III) aqua hydroxo complexes with cucurbit[6]uril. Russ. Chern. Bull., Int. Ed 2006,55, (2),267. 124. Coronado, E.; Gahin-Mascaros, J. R.; Gimenez-Saiz, c.; Gomez-Garcia, C. J.; Matinez-Ferrero, E.; Almeida, M.; Lopes, E. B., Metallic Conductivity in a Polyoxovandate Radical Salt ofBEDT-TTF: Synthesis, Structure and Physical Characterization. Adv. Mater. 2004, 16, 324. 125. Coronado, E.; Gimenez-Saiz, C.; Gomez-Garcia, C. J., Recent advances in polyoxometalate-containing molecular conductors. Coord Chern. Rev. 2005, 249, 1776. 126. Lapinski, A; Starodub, V.; Golub, M.; Kravchenko, A; Baumer, V.; Faulques, E.; Graja, A, Characterization and spectral Properties of the new organic metal (BEDT-TTF)6(Mos026)(DMFb). Synth. Met. 2003, 138,483. 127. Alley, K. G.; Bircher, R.; Waldmann, 0.; Ochsenbein, S. T.; Glidel, H. U.; Moubaraki, B.; Murray, K. S.; Fernandez-Alonso, F.; Abrahams, B. F.; Boskovic, C., Mixed-Valent Cobalt Spin Clusters: a Hexanuclear Complex and a One­ Dimensional Coordination Polymer Comprised ofAlternating Hepta- and Mononuclear Fragments. Inorg. Chern. 2006, 45, 8950. 245 128. Hyeon, T., Chemical synthesis of magnetic nanoparticles. Chern. Cornrnun. 2003, 927-934. 129. Kong, D.; Li, Y.; Ouyang, X.; Prosvirin, A V.; Zhao, H.; Ross, 1. H., Jr.; Dunbar, K. R; Clearfield, A, Syntheses, Structure, and magnetic Properties of New Types of Cu(IT), Co(II), and Mn(II) organophosphonates Materials: Three-Dimersonal Framworks and a one Dimersion Chain Motif. Chern. Mater. 2004, 16,3020. 130. Murugesu, M.; Anson, C. E.; Powell, A. K., Engineering of Ferrimagnetic CU12­ cluster arrays throught supramolecular interactions. Chern. Cornrnun. 2002, 1054­ 1055. 131. Tasiopoulos, A 1.; Vinslava, A; Wernsdorfer, W.; Abboud, K. A; Christou, G., Giant Single-Molecule Magnets: A {Mn84} Torus and Its Supramolecular Nanotubes. Angew. Chern. Int. Ed 2004,43,2117. 132. Viertelhaus, M.; Adler, P.; Clerac, R; Anaon, C. E.; Powell, A K., lron(II) Formate [Fe(02CH)2]-l/3HC02H: A Mesoporous Magnet Solvothermal Syntheses and Crystal Structures of the Isomorphous Framework Metal(II) Formates [M(02CHh]-n(Solvent) (M Fe, Co, Ni, Zn, Mg). Eur. J. Inorg. Chern. 2005,692. 133. Koizumi, S.; Nihei, M.; Shiga, T.; Nakano, M.; Nojiri, H.; Bircher, R; Waldmann, 0.; Ochsenbein, S. T.; Gudel, H. 0.; Fernandez-Alonso, F.; Oshio, H., A Wheel-Shaped Single-Molecule Magnet of [Mn(II)3Mn(III)4]: Quantum Tunneling of Magnetization under Static and Pulse Magnetic Fields. Chern. - Eur. J. 2007, 13, 8445. 134. Saalfrank, R W.; Scheurer, A; Prakash, R; Heinemann, F. W.; Nakajima, T.; Hampel, F.; Leppin, R; Pilawa, B.; Rupp, H.; Muller, P., Synthesis, Redox, and Magnetic Properties of a Neutral, Mixed-Valent Heptanuclear Manganese Wheel with S ) 27/2 High-Spin Ground State. Inorg. Chern. 2007,46, 1586. 135. Manoli, M.; Prescimone, A; Bagai, R; Mirshra, A; Murugesu, M.; Parsons, S.; Wernsdorfer, W.; Christou, G.; Brechin, E. K., High-Spin Mn Wheels. Inorg. Chern. 2007, 46, 6988. 136. Saalfrank, R W.; Deutscher, C.; Maid, H.; Ako, AM.; Sperner, S.; Nakajima, T.; Bauer, W.; Hampel, F.; Heb, B. A; van Eikema Hommes, N. 1. R; Puchta, R.; Heinemann, F. W., Synthesis, Structure, and Dynamics of Six-Membered Metallacoronands and Metallodendrimers of Iron and Indium. Chern. - Eur. J. 2004, 10, 1899. 246 137. Liu, Y.-B.; Duan, L.-M.; Yang, X.-M.; Xu, 1.-Q.; Zhang, Q.-B.; Lu, Y.-K; Liu, 1., Hydrothermal synthesis and characterization of two new bicapped Keggin heteropoly tungstovanadated derivatives. J. Solid State Chem. 2006, 179, 122. 138. Papaefstathiou, G. S.; Manessi, A.; Raptopoulou, C. P.; Terzis, A.; Zafiropoulos, T. F., Methanolysis as a Route to Gallium(III) Clusters: Synthesis and Structural Characterization of a Decanuc1ear Molecular Wheel. Inorg. Chem. 2006, 45, 8823. 139. King, P.; Stamatatos, T. c.; Abboud, K A.; Christou, G., Reversible Size Modification ofIron and Gallium Molecular Wheels: A GalO "Gallic Wheel" and Large GalS and FelS Wheels. Angew. Chem. Int. Ed. 2006, 45, 7379. 140. Salignac, B.; Riedel, S.; Dolbecq, A.; Secheresse, F.; Cadot, E., "Wheeling Templates" in Molecular Oxothiomolybdate Rings: Synthesis, Strcutures and Dynamics. J. Am. Chem. Soc. 2000, 122, 10381. 141. Briidgam, I.; Fuchs, 1.; Hartl, H.; Palm, R., Two new Isopolyoxotungstates(VI) with Empirical Composition CS2W207·2 H20 and Na2W207 • H20: and Icosatetratungstate and a Polymeric Compound. Angew. Chem. Int. Ed. 1998,37, 2668. 142. Salmon, L.; Thuery, P.; Ephritikhine, M., Polyhedron 2004,23, 623. 143. Modec, B.; Brencic, 1. V.; Koller, 1., Eur. J. Inorg. Chem. 2004, 1611. 144. Darensbourg, D. 1.; Gray, R. L.; De1ord, T., Inorg. Chem. Acta 1985, 98, L39. 145. Onoda, A.; Yamada, Y.; Okamura, T.; Doi, M.; Yamamoto, H.; Ueyama, N., J. Am. Chem. Soc. 2002, 124, 1052. 146. Wang, R.; Selby, H. D.; Liu, H.; Carducci, M. D.; Jin, T.; Zheng, Z.; Anthis, 1. W.; Staples, R. 1., Inorg. Chem. 2002,41,278. 147. Beattie, 1. K; Hambley, T. W.; Klepetko, J. A.; Masters, A. F.; Turner, P., Chem. Commun. 1998, 45. 148. Chen, Q.; Liu, S.; Zubieta, 1., Angew. Chem. Int. Ed. 1988,27, 1724. 149. Chen, Q.; Liu, S.; Zubieta, J., Inorg. Chem. 1989,28,4433. 150. Modec, B.; Dolenc, D.; Brencic, 1. V.; Koller, 1.; Zubieta, J., Eur. J. Inorg. Chem. 2005,3224. 247 151. Kessler, V. G.; Turova, N. Y.; Turevskaya, E. P., Inorg. Chern. Cornrnun. 2002,5, 549. 152. Kajiwara, T.; Wu, H.; Ito, T.; Iki, N.; Miyano, S., Octalanthanide Wheels Supported by p-tert-Butylsulfonylcalix[4]arene. Angew. Chern. Int. Ed 2004,43, 1832. Chapter II 1. Seichter, W.; Mogel, H.-1.; Brand, P.; Salah, D., Crystal Structure and Formation of the Aluminum Hydroxide Cloride [Al13(OHb(H20b]Chs • 13 H20. Eur. J. Inorg. Chern. 1998, 795-797. 2. Goodwin, J. C.; Teat, S. J.; Heath, S. L., How do clusters grow? The Synthesis and Structure ofPolynuclear Hydroxide Gallium(III) Clusters. Angew. Chern. Int. Ed 2004,43,4037-4041. 3. Jordan, P. A.; Clayden, N. J.; Heath, S. L.; Moore, G. R.; Powell, A. K.; Tapparo, A., Defining speciation profiles ofA13+complexed with small organic ligands: the At3+- heidi system. Coord Chern. Rev. 1996,149,281-309. 4. Gerasko, O. A.; Mainicheva, E. A.; Naumov, D. Y.; Kuratieva, N. V.; Sokolov, M. N.; Fedin, V. P., Synthesis and Crystal Structure of Unprecedented Oxo/Hydroxo-Bridged Polynuclear Gallium(III) Aqua Complexes. Inorg. Chern. 2005,44,4133. 5. Casey, W. H., Large Aqueous Aluminum Hydroxide Molecules. Chern. Rev. 2006, 106, 1. 6. Mainicheva, E. A.; Gerasko, O. A.; Sheludyakova, L. A.; Naumov, D. Y.; Naumova, M. I.; Fedin, V. P., Synthesis and crystal structures ofsupramolecular compounds ofpolynuclear alurninum(III) aqua hydroxo complexes with cucurbit[6]uril. Russ. Chern. Bull., Int. Ed 2006,55, (2),267. 7. Schmitt, W.; Baissa, E.; Mandel, A.; Anson, C. E.; Powell, A. K., [Ahs(~3­ O)4(~3-0HM~-OH)14(hpdta)3t - A New Ahs Aggergate Which forms a Suprmolecular Zeotype. Angew. Chern. Int. Ed 2001, 40,3578-3581. 8. Hagrman, P. 1.; Finn, R. C.; Zubieta, J., Soild State Sci. 2001,3, 745-774. 9. Crawford, N. R. M.; Long, 1. R, Inorg. Chern. 2001, 40, 3456-3462. 248 10. Michot, L. J.; Montarges-Pelletier, E.; Lartiges, B. S.; de la Caillerie, J.-B. d. E.; Briois, L., Fonnation Mechanism of the Ga13 Keggin Ion: A combined EXFAS and NMR Study. J. Am. Chem. Soc. 2000,122,6048-6056. 11. Allouche, L.; Gerardin, C.; Loiseau, T.; Ferey, G.; Taulelle, F., Abo: Giant AluminumPolycation.Angew. Chem. Int. Ed 2000,39,511-514. 12. Schmitt, W.; Jordan, P. A; Henderson, R. K; Moore, G. R; Anson, C. E.; Powell, A K, Synthesis, Structure and Properties of hydrolytic Al(III) aggregates and Fe(III) analogues fonned with iminodiacetate-based chelating ligands. Coord Chem. Rev. 2002,228, 115-126. 13. Casey, W. H.; Phillips, B. L.; Furrer, G., Aqueous Aluminum Polynuclear Complexes and Nanoclusters: A Review. In Reviews in Mineralogy & Geochemistry, Mineralogical Society of America: Washington D.C., 2001; Vol. 44, pp 167-190. 14. Rowsell, 1.; Nazar, L. F., Speciation and Thennal Transformation in Alumina Sols: Structures of the Polyhydroxoaluminum Cluster [Abo08(OH)56(H20h6]18+ and its 8-Keggin Moiete. J. Am. Chem. Soc. 2000,122,3777-3778. 15. Harris, W. R; Messori, L., A comparative study of aluminum(III) , gallium(III), indium(III), and thallium(III) binding to human serum transferrin. Coord. Chem. Rev. 2002,228,237-262. 16. Alvisiatos, A; Barbara, P. F.; Castleman, A W.; Chang, J.; Dixon, D. A; Klein, M. L.; Mclendon, G. L.; MIller, J. S.; Ratner, M. A; Rossky, P. J.; Stupp, S. 1.; Thompson, M. E., From Molecules to Materials: Current Trends And Future Directions. Adv. Mater. 1998,10, 1297-1336. 17. Bradley, S. M.; Kydd, R. A; Yamdagni, R, Detection of a new Polymeric species fonned through the Hydrolysis of Gallium(III) Salt Solutions. J. Chem. Soc. Dalton Trans. 1990,413-417. 18. Bradley, S. M.; Kydd, R A, Comparison of the Species formed Upon Base Hydrolyses of Gallium(III) adn lron(III) Aqueous Solutions: The Possibility of Existence of an [Fe04Feu(OHb(H20)12f+ polyxoxocation. J. Chem. Soc. Dalton Trans. 1993,2407-2413. 19. Heath, S. L.; Jordan, P. A; Johnson, 1. D.; Moore, G. R.; Powell, A K; Helliwell, M., Comparative X-ray and 27Al NMR Spectroscopic Studies of the Speciation of Aluminum in Aqueous Systems: Al(III) Complexes of N(CH2C02H)2(CH2CH20H). J. Inorg. Biochem. 1995, 59, 785-794. 249 20. Velikorodov, A V., Zh. Org. Kim. 2000,36,256-262. 21. Maleski, R. J.; Kluge, M.; Sicker, D., Synth. Commun. 1995,25,2327-2335. 22. Raphael, R. A; Ravenscroft, P., J. Chem. Soc. Perkin Trans. 11988, 1823-1825. 23. Johansson, G., Acta Chem. Scand 1960,14, 771-773. 24. Schonherr, S., Anorg. AUg. Chem. 1983, 503, 37-42. Chapter III 1. Rather, E.; Gatlin, J. T.; Nixon, P. G.; Tsukamoto, T.; Kravtsov, V.; Johnson, D. W., A Simple Organic Reaction Mediates the Crystallization of the Inorganic Nanocluster [Ga13(J.!3-0HMJ.l2-0H)I8(H20)24](N03)IS. J. Am. Chem. Soc. 2005, 127,3242-3243. 2. Dieterich, D. A; Paul, 1. c.; Curtin, D. Y., Structural Studies on Nitrosobenzene and 2-Nitrosobenzoic Acid. Crystals and Molecular Structures of cis-Azobenzene Dioxide and trans-2,2'-Dicarboxyazobenzene Dioxide. J. Am. Chem. Soc. 1974, 96,6372. 3. Cambridge Structural Database, Cambridge Crystallographic Data Centre: 12 Union Road, Cambridge, CB2 1EZ, UK, November 2006. 4. In Langs Handbook ofChemistry, 15th ed.; Dean, J. A, Ed. McGraw Hill: 1999; p 8153. 5. Okabe, N.; Tamaki, K.; Suga, T.; Kohyama, Y., Aluminium Cupferronate, [AI(C6HsN20 2)3]' Acta Cryst. 1995, C51, 1295. 6. Casey, W. H., Large Aqueous Aluminum Hydroxide Molecules. Chem. Rev. 2006, 106, 1. 7. Mainicheva, E. A; Gerasko, O. A.; Sheludyakova, L. A; Naumov, D. Y.; Naumova, M. 1.; Fedin, V. P., Synthesis and crystal structures of supramolecular compounds of polynuclear aluminum(III) aqua hydroxo complexes with cucurbit[6]uril. Russ. Chem. Bull., Int. Ed. 2006, 55, (2),267. 8. Merck Index. 11th ed.; 1989. 250 9. Chellamani, A; Suresh, R, Kinetics and Mechanism of Oxidation of Triphenylphosphine by hydrogen-Peroxide. Reac. Kinet. Cat. Lett. 1988,37, (2), 501. 10. Srinivasan, C.; Chellamani, A., Kinetics of Oxidation of Triarylasines by Potassium Peroxodisulfate. Indian J. Chem. Sec. A 1984, 23A, 684. 11. Srinivasan, c.; Pitchumani, K., Mechanism of the Oxidation of Triphenyl Derivatives ofP, As, and Sb by Peroxodiphospahte. Can. J. Chem. 1985,63, (8), 2285. 12. Hasbrouck, L. J.; Carlin, C. M.; Risley, J. M., Origin of the oxygen in the oxidation of triphenylphosphine by potassium perphosphate. Inorg. Chem. Acta 1997,258, (1), 123. 13. Copley, D. B.; Fairbrother, F.; Miller, 1. R; Thompson, A, The Oxidation of Triphenylphosphine with Hydrogen Peroxide. Proc. Chem. Soc. 1964, 300. 14. Arbuzov, B. A, Oxidation of organic compounds with peracetic and perbenzoic acids. Journaljuer Praktische Chemie 1931,131,357. 15. Glidewell, C.; Harris, G. S.; Holden, H. D.; Liles, D. c.; McKechnie, 1. S., J. Fluorine Chem. 1981, 18, 143. 16. Beagley, B.; El-Sayrafi, 0.; Gott, G. A; Kelly, D. G.; McAuliffe, C. A; Mackie, A G.; MacRory, P. P.; Pritchard, R G., J. Chem. Soc. Dalton Trans. 1988, 1095. 17. Calleri, M.; Ferguson, G., Cryst. Struct. Commun. 1972, 1,331. 18. Weitze, A; Henshel, D.; Blaschette, A; Jones, P. G., Z. Anorg. AUg. Chem. 1995, 621, 1746. 19. Goodwin, J. c.; Teat, S. J.; Heath, S. L., How do clusters grow? The Synthesis and Structure of Polynuclear Hydroxide Gallium(III) Clusters. Angew. Chem. Int. Ed. 2004,43,4037-4041. 20. Allouche, L.; Gerardin, c.; Loiseau, T.; Ferey, G.; Taulelle, E, A130 : Giant Aluminum Polycation. Angew. Chem. Int. Ed. 2000,39,511-514. 21. Casey, W. H.; Phillips, B. L.; Furrer, G., Aqueous Aluminum Polynuclear Complexes and Nanoclusters: A Review. In Reviews in Mineralogy & Geochemistry, Mineralogical Society of America: Washington D.C., 2001; Vol. 44, pp 167-190. 251 22. Rowsell, J.; Nazar, L. E, Speciation and Thermal Transformation in Alumina Sols: Structures of the Polyhydroxoaluminum Cluster [A1300 8(OH)S6(H20)26]18+ and its a-Keggin Moiete. J. Am. Chem. Soc. 2000, 122,3777-3778. 23. Schmitt, W.; Baissa, E.; Mandel, A; Anson, C. E.; Powell, A K., [Alls(Jl3-0MJl3­ OH)6(Jl-OH)lihpdta)3t - A New AIls Aggergate Which forms a Suprmolecular Zeotype. Angew. Chem. Int. Ed. 2001,40,3578-3581. 24. Schmitt, W.; Jordan, P. A; Henderson, R. K.; Moore, G. R.; Anson, C. E.; Powell, A K., Synthesis, Structure and Properties of hydrolytic Al(III) aggregates and Fe(III) analogues formed with iminodiacetate-based chelating ligands. Coord. Chem. Rev. 2002,228, 115-126. 25. Seichter, W.; Mogel, H.-J.; Brand, P.; Salah, D., Crystal Structure and Formation of the Aluminum Hydroxide Cloride [Al13(OH)24(H20)24]Clls • 13 H20. Eur. J. Inorg. Chem. 1998, 795-797. 26. Heath, S. L.; Jordan, P. A; Johnson, I. D.; Moore, G. R.; Powell, A K.; Helliwell, M., Comparative X-ray and 27Al NMR Spectroscopic Studies of the Speciation of Aluminum in Aqueous Systems: Al(III) Complexes of N(CH2C02HMCH2CH20H). J. Inorg. Biochem. 1995,59,785-794. 27. Casey, W. H.; Olmstead, M. M.; Phillips, B. L., A New Aluminum Hydroxide Octamer, [Alg{OH)liH20)18](S04)s·16H20. Inorg. Chem. 2005,44,4888. 28. Johansson, G., Acta Chem. Scand. 1960, 14, 771-773. 29. Lee, A P.; Phillips, B. L.; Olmstead, M. M.; Casey, W. H., Synthesis and Characterization of the Ge04Al12(OH)2iOH2)12 8+Polyoxocation. Inorg. Chem. 2001, 40, 4485. 30. Casey, W. H.; Phillips, B. L., Kinetics of oxygen exchange between sites in the Ga04Al12(OH)24(H20)12 7+(aq) molecule and aqueous solution. Geochimica et Cosmochimica Acta 2001, 65, (5), 705. 31. Gerasko, 0. A; Mainicheva, E. A; Naumov, D. Y.; Kuratieva, N. V.; Sokolov, M. N.; Fedin, V. P., Synthesis and Crystal Structure of Unprecedented Oxo/Hydroxo-Bridged Polynuclear Gallium(III) Aqua Complexes. Inorg. Chem. 2005,44,4133. 32. Wulfsberg, G., University Science Books: Sausalito, CA, 2000; P 59. 33. Gatlin, J. T.; Mensinger, Z. L.; Meyers, S. T.; Zakharov, L. N.; Keszler, D. A; M; Johnson, D. W., Heterometallic Group 13 Keggin-like Nanoclsuters. Manuscript in preparation. 252 34. Anderson, J. S., Constitution of the Poly-acids. Nature 1937, 140,850. 35. Evans, H. T., Jr, The Crystal Structures of Ammoium and Potassium Molydotellurates. J. Am. Chem. Soc. 1948,70, (3), 1291. 36. Van der Sluis, P.; Spek, A L., BYPASS: an effective method for the refinement of crystal structures containing disordered solvent regions. Acta Cryst. 1990, A46, 194-201. Chapter IV 1. Seichter, W.; Mogel, H.-I.; Brand, P.; Salah, D., Crystal Structure and Formation of the Aluminum Hydroxide Cloride [Al13(OH)24(H20)24]Chs • 13 H20. Eur. J. Inorg. Chem. 1998, 795-797. 2. Heath, S. L.; Jordan, P. A; Johnson, 1. D.; Moore, G. R; Powell, A K.; Helliwell, M., Comparative X-ray and 27Al NMR Spectroscopic Studies of the Speciation of Aluminum in Aqueous Systems: Al(III) Complexes of N(CH2C02H)2(CH2CH20H). J. Inorg. Biochem. 1995, 59, 785-794. 3. Goodwin, I. C.; Teat, S. J.; Heath, S. L., How do clusters grow? The Synthesis and Structure ofPolynuclear Hydroxide Gallium(III) Clusters. Angew. Chem. Int. Ed 2004,43,4037-4041. 4. Rather, E.; Gatlin, I. T.; Nixon, P. G.; Tsukamoto, T.; Kravtsov, V.; Johnson, D. W., A Simple Organic Reaction Mediates the Crystallization of the Inorganic Nanocluster [Gal3(1!3-0H)6(1!2-0H)18(H20b](N03)lS. J. Am. Chem. Soc. 2005, 127, 3242-3243. 5. Gatlin, I. T.; Mensinger, Z. L.; Meyers, S. T.; Zakharov, L. N.; Keszler, D. A; Johnson, D. W., Heterometallic Group 13 Keggin-like Nanoclsuters. Manuscript in preparation. 6. Gerasko, O. A; Mainicheva, E. A; Naumov, D. Y; Kuratieva, N. V.; Sokolov, M. N.; Fedin, V. P., Synthesis and Crystal Structure of Unprecedented Oxo/Hydroxo-Bridged Polynuclear Gallium(III) Aqua Complexes. Inorg. Chem. 2005,44, 4133. 7. Casey, W. H.; Olmstead, M. M.; Phillips, B. L., A New Aluminum Hydroxide Octamer, [Alg{OH),iH20),8](S04)s·16H20. Inorg. Chem. 2005,44,4888. 253 8. Gatlin, l T.; Mensinger, Z. L.; Zakharov, L. N.; MacInnes, D.; Johnson, D. W., Facile Synthesis of Aluminum13 Keggin-Like Nanoc1uster. Inorg. Chern. manuscript accepted. 9. Bradley, S. M.; Kydd, R. A, Comparison of the Species formed Upon Base Hydrolyses of Gallium(III) adn Iron(III) Aqueous Solutions: The Possibility of Existence of an [Fe04Fen(OHb(H20)12f+ polyxoxocation. J. Chern. Soc. Dalton Trans. 1993,2407-2413. 10. Bradley, S. M.; Kydd, R. A; Yamdagni, R, Detection of a new Polymeric species formed through the Hydrolysis of Gallium(III) Salt Solutions. J. Chern. Soc. Dalton Trans. 1990,413-417. 11. Kudynska, J.; Buckmaster, H. A; Kawano, K.; Bradley, S. M.; Kydd, R A, A 9 GHz cw-electron-paramagnetic resonance study of the sulphate salts of tridecameric [MnxAl13•x0 4(OHb(H20)12](7-x). J. Chern. Phys. 1993,99,3329. 12. Oszk6, A; Kiss, J.; Kiricsi, 1., XPS investigations on the feasibility of isomorphous substitution of octahedral At3+ for Fe3+ in Keggin ion salts. Phys. Chern. Chern. Phys. 1999,1,2565. 13. Parker, W.O., Jr.; Millini, R; Kiricsi, 1., Metal Substitution in Keggin-Type Tridecameric Aluminum-Oxo-Hydroxy Clusters. Inorg. Chern. 1997,36,571. 14. Nsouli, N. H.; Bassil, B. S.; Dickman, M. H.; Kortz, U.; Keita, B.; Nadjo, L., Synthesis and Structure of Dilacunary Decatungstogermanate, [g-GeWI0036t. Inorg. Chern. 2006, 45, 3858. 15. Wang, l-P.; Zhao, J.-W.; Duan, X.-Y.; Niu, l-Y., Syntheses and Structures of One- and Two-Dimensional Organic-Inorganic Hybrid Rare Earth Derivatives Based on Monovacant Keggin-Type Polyoxotungstates. Cryst. Growth Des. 2006, 6, (2), 507. 16. Lee, A P.; Furrer, G.; Casey, W. H., On the Acid-Base Chemistry of the Keggin Polymers: GaAh2 and GeAh2. J. Colloid Interface Sci. 2002,250,269. 17. Cowan, J. l; Bailey, A. J.; Heintz, R A; Do, B. T.; Hardcastle, K. 1.; Hill, C. L.; Weinstock, 1. A, Formation, Isomerization, and Derivatization of Keggin Tungstoaluminates. Inorg. Chern. 2001, 40, 6666. 18. Carrier, x.; de la Caillerie, l-B. d. E.; Lambert, l-F.; Che, M., The Support as a Chemical Reagent in the Preparation ofWOx/g-Ah03 Catalysts: Formation and Deposition of Aluminotungstic Heteropolyanions. J. Arn. Chern. Soc. 1999, 121, 3377. 254 19. Lee, A. P.; Phillips, B. L.; Olmstead, M. M.; Casey, W. H., Synthesis and Characterization of the Ge04Ahz(OH)24(OHZ)12 8+ Polyoxocation. Inorg. Chem. 2001, 40, 4485. 20. Heath, S. L.; Powell, A. K, The Trapping ofIron Hydroxide Units by the Ligand "HEIDI"; Two new Hydroxo(oxo)iron Clusters Containing 19 and 17 Iron Atoms. Angew. Chem. Int. Ed. 1992,31, 191. 21. Chiang, H. Q.; Hong, D.; Hung, C. M.; Presley, R E.; Wager, J. F.; Park, C.-H.; Keszler, D. A.; Herman, G. S., Thin-film transistors with amorphous indium gallium oxide channel layers. 1. Vac. Sci. Technol. 2006, 24, 2702. 22. Presley, R. E.; Honga, D.; Chianga, H. Q.; Hunga, C. M.; Hoffmanb, R L.; Wager, 1. F., Transparent ring oscillator based on indium gallium oxide thin-film transistors. SoUd State Electronics 2006, 50, 500. 23. Nomura, K; Ohta, H.; Takagi, A; Kamiva, T.; Hirano, M.; Hosono, H., Room­ temperature fabrication of transparent flexibi1e thin-film trasistors using amorphous oxide semicondutors. Nature 2004, 432, 488. 24. Anderson, 1. T.; Munsee, C.; Hung, C. M.; Phung, T. M.; Johnson, D. c.; Herman, G. S.; Wager, 1. F.; Kesz1er, D. A, Adv. Funct. Mater. in press. 25. Meyers, S. T.; Anderson, 1. T.; Hong, D.; Hung, C. M.; Wager, J. F.; Kesz1er, D. A., Chem. Mater. in press. Chapter V 1. Li, c.; Lai, M. Y. D.; Leong, W. K, ToF-SIMS analysis of surface-anchored organometallic clusters. J. Organometallic Chem. 2005, 690, 2861. 2. Nazmutdinov, R R; Zinkicheva, T. T., Russ. 1. Electrochem. 2004,40, (4), 379. 3. Rostam-Khani, P.; Philipsen, J.; Jansen, E.; Eberhard, H.; Vullings, P., Appl. Surf Sci. 2006,252, 7255. 4. Schroder-Oeynhausen, F.; Burkhardt, B.; Fladung, T.; Kotler, F.; Schnieders, A; Wiedmann, L.; Benninghoven, A., 1. Vac. Sci. Technol. 1998, 16, 1002. 5. Aubriet, F.; Poleunis, c.; Bertrand, P., Investigation of the cluster ion formation process for inorganic compounds in static SIMS . Appl. Surf Sci. 2003, 203, 114. 255 6. Graham, D. J.; Wagner, M. S.; Castner, D. G., Information from complexity: Challenges of TOF-SIMS data interpretation. Appl. Surf Sci. 2006, 252, 6860. 7. Sein, L. T., Jr., Using Punnett Squares To Facilitate Students' Understanding of Isotopic Distributions in Mass Spectrometry. J. Chern. Ed 2006, 83, 228. 8. Li, Z.; Hirokawa, K., Ga+ Primary Ion ToF-SIMS Fragment Pattern ofMetals and Inorganic Compounds. Anal. Sci. 2003, 19, 1231. 9. Li, Z.; Hirokawa, K., Ga+ Primary Ion ToF-SIMS fragment pattern of inorganic compounds and Metals. Appl. Surf Sci. 2003,220, 136. 10. Casey, W. H.; Olmstead, M. M.; Phillips, B. L., A New Aluminum Hydroxide Octamer, [Alg(OH)14(H20)lg](S04)s·16H20. Inorg. Chern. 2005,44,4888. 11. Goodwin, l C.; Teat, S. J.; Heath, S. L., How do clusters grow? The Synthesis and Structure of Polynuclear Hydroxide Gallium(III) Clusters. Angew. Chern. Int. Ed. 2004,43,4037-4041. 12. CAChe CAChe, 6.1.1; Fujitsu Limitied, Inc.: U.S.A., 2001. 13. Garrison, B. J.; Winograd, N.; Harrison, D. E., Jr., Atomic and Molecular ejection from ion-bombarded reacted single-crystals surfaces. Oxygen on Copper(100). Phys. Rev. B 1978, 18, (11), 6000. 14. Colton, R. J., Molecular seconday ion mass spectrometry (SIMS). J. Vac. Sci. Technol. 1981, 78, 737. 15. Garrison, B. l; Winograd, N.; Harrison, D. E., Jr., Formation of Small Metal Clusters by ion bombardment of Single crystal surfaces. J. Chern. Phys. 1978, 69, (4), 1440. 16. Pachuta, S. J.; Cooks, R. G., Mechanisms in Molecular SIMS. Chern. Rev. 1987, 87,647. 17. Wucher, A.; Garrison, B. l, Cluster formation in sputtering: A molecular dynamics study using the MDIMC corrected Effective medium Potential. J. Chern. Phys. 1996, 105, 5999. 18. Wucher, A., Internal Energy of Sputtered Metal Clusters. Phys. Rev. B 1994, 49, (3),2012. 256 19. Wucher, A.; Garrison, B. J., Unimolecular Decomposition in the sputtering of metal clsuters. Phys. Rev. B 1992,46, (8), 4855. 20. Anderson, J. T.; Munsee, c.; Hung, C. M.; Phung, T. M.; Johnson, D. C.; Herman, G. S.; Wager, l F.; Keszler, D. A., Adv. Funct. Mater. in press. 21. Meyers, S. T.; Anderson, l T.; Hong, D.; Hung, C. M.; Wager, J. F.; Keszler, D. A., Chem. Mater. in press. 22. Brauman, J. 1., Least Squares Analysis and Simplification of Multi-Isotope Mass Spectra. Anal. Chem. 1966, 38, 607. Chapter VI 1. Yan, C.-H.; He, c.; Wang, L.-Y.; Wang, Z.-M.; Liu, Y.; Liao, c.-S., Self­ assembly of tetrahedral M4L6 clusters from a new rigid ligand. J Chem. Soc., Dalton Trans. 2002, 134. 2. Rice, C. R; Baylies, C. l; Clayton, H. l; Jeffery, J. c.; Paul, R L.; Ward, M. D., Novel multidentate pyridyl/thiazolylligands containing terpyridine units: formation of dinuclear and trinuclear double helicate complexes. Inorganica Chimica Acta 2003,351,207-216. 3. Rice, C. R; Worl, S.; Jeffery, J. c.; Paul, R. L.; Ward, M. D., New multidentate ligands for supramolecular coordination chemistry: double and triple helical complexes of ligands containing pyridyl and thiazolyl donor units. J Chem. Soc., Dalton Trans. 2001, (5), 550-559. 4. Bell, Z. R.; McCleverty, J. A.; Ward, M. D., New Multidentate Pyrazolyl­ Pyridine Ligands - Syntheis and Structures. Aust. J Chem. 2003,56,665. 5. Paul, R L.; Bell, Z. R.; Fleming, l S.; Jeffery, J. C.; McCleverty, l A.; Ward, M. D., Self-Assembly of Anion-Binding Supramolecular Cage Complexes. Heteroatom Chemistry 2002, 13, (6),567. 6. Saalfrank, R W.; Bernt, 1.; Chowdhry, M. M.; Hampel, F.; Vaughan, G. B. M., Ligand-to-Metal Ratio Controlled Assembly of Tetra- and Hexanuclear Clusters Towards Single-Molecule Magnets. Chem. Eur. J 2001,7,2765. 7. Saalfrank, R W.; Demleitner, B.; Glaser, H.; Maid, H.; Bathelt, D.; Hampel, F.; Bauer, W.; Teichert, M., Enantiomerisation of Tetrahedral Homochiral [M4L6l Clusters: Synchronised Four Bailar Twists and SixAtropena ntiomerisation Processes Monitored by Temperature-Dependent Dynamic IH NMR Spectroscopy. Chem. Eur. J. 2002, 8, 2679. 257 8. Saalfrank, R W.; Glaser, H.; Demleitner, B.; Hampel, F.; Chowdhry, M. M.; Schunemann, V.; Trautwein, A X.; Vaughan, G. B. M.; Yeh, R; Davis, A V.; Raymond, K. N., Self-Assembly of Tetrahedral and Trigonal Antiprismatic Clusters [FeiL4)4] and [Fe6(Ls)6] on the Basis of Trigonal Tris-Bidentate Chelators. Chem. Eur. J. 2002, 8, 493. 9. Saalfrank, R W.; Reimann, U.; Goritz, M.; Hampel, F.; Scheurer, A; Heinemann, F. W.; Buschel, M.; Daub, J., Metal- and Ligand-Directed One-Pot Syntheses, Crystal Structures, and Properties of Novel Oxo-Centered Tetra- and Hexametallic Clusters. Chem. Eur. J. 2002, 8, 3614. 10. CAChe Cache Quantum, 6.1.1; Fujitsu Limited: 2001. 11. Bell, Z. e. R; Jeffery, J. c.; McCleverty, J. A; Ward, M. D., Assembly of a Truncated-Tetrahedral Chiral [M12(jl-L)lSf4 + Cage. Angew. Chem. Int. Ed. 2002, 41,2515. 12. Biradha, K.; Seward, c.; Zaworotko, M. J., Helical Coordination Polymers with Large Chiral Cavities. Angew. Chem. Int. Ed. 1999, 38, 492. 13. Paul, R L.; Couchman, S. M.; Jeffery, J. c.; McCleverty, J. A.; Reeves, Z. R; Ward, M. D., Effects of metal co-ordination geometry on self-assembly: a dinuclear double helicate complex and a tetranuclear cage complex of a new bis­ bidentate bridging ligand. J. Chem. Soc., Dalton Trans. 2000, 845. 14. Saalfrank, R W.; Low, N.; Trummer, S.; Sheldrick, G. M.; Teichert, M.; Stalkec, D., Octanuclear Bis(triple-helical) Metal(II) Complexes. Eur. J. Inorg. Chem. 1998,559. 15. Saalfrank, R W.; Schmidt, c.; Maid, H.; Hampel, F.; Bauer, W.; Scheurer, A, Enantimericaly Pure Copper (In Cubanes [Cu4~(OMe)4] from Chiral Bis-l,3­ diketones H2L through Diastereoselective Self-Assembly. Angew. Chem. Int. Ed 2006,45,315. AppendixB 1. SAINT, S. A D. I. P., Bruker AXS, Inc., Madison, 1995. 2. G. M. Sheldrick, S., Bruker AXS, Inc., WI, USA, 1997 SHELXTL. 3. G. M. Sheldrick, B. A, Inc., WI, USA, 1996, SADABS. 258 AppendixD 1. Chen, Z.; Zhou, Y.; Weng, L.; Zhang, H.; Zhao, D., Hydrothennal synthesis of two layered indium oxalates with 12-membered apertures. J. Solid State Chem. 2003, 173,435. 2. Rather, E.; Gatlin, J. T.; Nixon, P. G.; Tsukamoto, T.; Kravtsov, V.; Johnson, D. W., A Simple Organic Reaction Mediates the Crystallization of the Inorganic Nanocluster [Ga13(!l3-0H)6(!l2-0H)18(H20b](N03)15. J. Am. Chem. Soc. 2005, 127, 3242-3243. 3. Van der Sluis, P.; Spek, A L., BYPASS: an effective method for the refinement of crystal structures containing disordered solvent regions. Acta Cryst. 1990, A46, 194-201. Appendix G 1. Steed, J. W.; Atwood, J. L. Supramolecular Chemistry; Wiley, 2000. 2. Garrett, R. H.; Grisham, C. M. Biochemistry; 2nd ed.; Saunders College Publishing: Orlando, Flordia, 1999. 3. Lehn, J. M. Rep. Prog. Phys. 2004, 67, 249. 4. Chambron, J.-c.; Collin, J.-P.; Heitz, V.; Jouvenot, D.; Kern, J.-M.; Mobian, P.; Pomeranc, D.; Sauvage, J.-P. Eur. J. Org. Chem. 2004, 1627. 5. Leigh, D. A; Lusby, P. J.; Teat, S. J.; Wilson, A J.; Wong, J. K Y. Angew. Chem. Int. Ed 2001,40, 1538. 6. Kaiser, G.; Jarrosson, T.; Otto, S.; Ng, Y-F.; Bond, A D.; Sanders, J. K M. Angew. Chem. Int. Ed 2004, 43, 1959. 7. Hogg, L.; Leigh, D. A; Lusby, P. J.; Morelli, A; Parsons, S.; Wong, J. K Y. Angew. Chem. Int. Ed 2004,43,1217. 8. Hasenknopf, B.; Lehn, J.-M.; Boumediene, N.; Leize, E.; Dorsselaer, A V. Angew. Chem. Int. Ed 1998,37,3265. 9. Ibukuro, F.; Fujita, M.; Yamaguchi, K; Sauvage, J.-P. J. Am. Chem. Soc. 1999, 121, 11014. 259 10. Feyter, S. D.; Abdel-Mottaleb, M. M. S.; Schuurmans, N.; Verkuijl, B. J. V.; Esch, J. H. v.; Feringa, B. L.; Schryver, F. C. D. Chern. Eur. J. 2004,10, 1124. 11. Saalfrank, R W.; Trummer, S.; Reimann, U; Chowdhry, M. M.; Hampel, F.; Waldmann, O. Angew. Chern. Int. Ed. 2000, 3492. 12. Saalfrank, R W.; Glaser, H.; Demleitner, B.; Hampel, F.; Chowdhry, M. M.; Schfulemann, V.; Trautwein, A x.; Vaughan, G. B. M.; Yeh, R; Davis, A V.; Raymond, K. N. Chern. Eur. J. 2002, 8, 493. 13. Yoshizawa, M.; Kusukawa, T.; Fujita, M.; Sakamoto, S.; Yamaguchi, K. J. Arn. Chern. Soc. 2001,123, 10454-10459. 14. Yoshizawa, M.; Takeyama, Y.; Kusukawa, T.; Fujita, M. Angew. Chern. Int. Ed. 2002, 41, 1347. 15. Sanmartin, J.; Bermejo, M. R.; Garcia-Deibe, A M.; Rivas, 1. M.; Fernandez, A R J. Chern. Soc., Dalton Trans. 2000,4174. 16. Muller, 1.; Spillmann, S.; Franck, H.; Pietschnig, R Chern. Eur. J. 2004, 10,2207. 17. Saalfrank, R W.; Maid, H.; Mooren, N.; Hampel, F. Angew. Chern. Int. Ed 2002, 41,304. 18. Bell, Z. e. R; Jeffery, J. C.; McCleverty, J. A; Ward, M. D. Angew. Chern. Int. Ed 2002,41,2515. 19. Yan, C.-H.; He, C.; Wang, L.-Y.; Wang, Z.-M.; Liu, Y.; Liao, c.-S. J. Chern. Soc., Dalton Trans. 2002, 134. 20. Holliday, B. J.; Mirkin, C. A Angew. Chern. Int. Ed 2001,40,2022. 21. Gavrilova, A L.; Bosnich, B. Chern. Rev. 2004, 104, 349. 22. Fujita, M. Chern. Soc. Rev. 1998,27,417. 23. Field, J. E.; Combariza, M. Y.; Vacheta, R W.; Venkataraman, D. Chern. Cornrnun. 2002,2260. 24. Comba, P.; Schiek, W. Coord Chern. Rev. 2003,238-239,21. 25. Saalfrank, R W.; Uller, E.; Demleitner, B.; Bernt, 1. Structure & Bonding 2000, 96, 149. 260 26. Fekner, T.; Gallucci, J.; Chan, M. K Org. Lett. 2004, 6,989. 27. Boswell, C. A.; Sun, X.; Niu, W.; Weisman, G. R; Wong, E. H.; Rheingold, A. L.; Anderson, C. J. J. Med. Chem. 2004,47, 1465. 28. Aime, S.; Cavallotti, C.; Gianolio, E.; Giovenzana, G. B.; Palmisano, G.; Sisti, M. Org. Lett. 2004, 6, 1201. 29. Lu, T.; Zhuang, X; Li, Y.; Chen, S. J. Am. Chem. Soc. 2004,126,4760. 30. Jiang, P.; Guo, Z. Coord. Chem. Rev. 2004,248,205. 31. Baret, P.; Einhorn, J.; Gellon, G.; Pierre, J.-L. Synthesis 1998,431. 32. CAChe; 6.1.1 ed.; Fujitsu Limited, 2001. 33. Dong, G.; Pang, K-1.; Duan, C.-y.; Cheng, H.; Meng, Q.-j. Inorg. Chem. 2002, 41,5978-5985. 34. Hu, Y.-Z.; Zhang, G.; Thummel, R P. Org. Lett. 2003,5,2251. 35. CSD In Cambridge Structure Database System; Cambridge Cryastallographic Data Centre. 36. CAJ and Eric Synthesis note 37. Isobe, T.; Ishikawa, T. J. Org. Chem. 1999,64,6984. 38. James S. Fleming; Karen L. V. Mann; Charles-Antoine Carraz; Elefteria Psillakis; Jeffery, 1. C.; McCleverty, J. A.; Ward, M. D. Angew. Chem. Int. Ed. 1998,37, 1279. 39. Paul, R L.; Bell, Z. R; Jeffery, 1. C.; Harding, L. P.; McCleverty, J. A.; Ward, M. D. Polyhedron 2003, 22, 781. 40. Gong, 1.; Gibb, B. C. Org. Lett. 2004, 6, 1353. 41. Akermark, B.; Bjernemose, 1.; Borje, A.; Chmielewski, P. 1.; Paulsen, H.; Simonsen, 0.; Stein, P. C.; Toftlund, H.; Wolny, J. A. J. Chem. Soc., Dalton Trans. 2004, 1215. 42. Colasson, B. X; Sauvage, J.-P. Inorg. Chem. 2004,43, 1895. 43. Brooker, S.; Iremonger, S. S.; Plieger, P. G. Polyhedron 2003, 22, 665. 261 44. Shepherd, R. E. Coord Chern. Rev. 2003,247, 147. 45. Biradha, K.; Seward, c.; Zaworotko, M. J. Angew. Chern. Int. Ed 1999,38,492. 46. Saalfrank, R W.; Maid, H.; Hampel, F.; Peters, K. Eur. J. Inorg. Chern. 1999, 1859. 47. Tavacoli, S.; Miller, T. A.; Paul, R L.; Jeffery, J. c.; Ward, M. D. Polyhedron 2003,22, 507. 48. Stiriba, S.-E.; Frey, H.; Haag, R Angew. Chern. Int. Ed 2002,41, 1329. 49. Schmittel, M.; Kalsani, V.; Fenskeb, D.; Wiegrefea, A. Chern. Cornrnun. 2004, 490. 50. Uppadine, L. H.; Gisselbrechtb, J.-P.; Lehn, J.-M. Chern. Cornrnun. 2004, 718. 51. Nitschke, J. R; Lehn, J.-M. Proc. Nat!. Acad Sci. USA 2003, 100, 11970. 52. Hasenknopf, B.; Lehn, J.-M.; Boumediene, N.; Emmanuelle Leize; Dorsselaer, A. V. Angew. Chern. Int. Ed 1998,37,3265. 53. Hogarth, G.; Humphrey, D. G.; Kaltsoyannis, N.; Kim, W.-S.; Lee, M.-y. V.; Norman, T.; Redmond, S. P. J. Chern. Soc., Dalton Trans. 1999,2705. 54. Zhu, H.-L.; Tong, Y.-X.; Chen, X.-M. J. Chern. Soc., Dalton Trans. 2000,4182. 55. Charbonniere, L. J.; Williams, A. F.; Piguet, c.; Bernardinelli, G.; Rivara-Minten, E. Chern. Eur. J. 1998,4,485. 56. Piguet, c.; Edder, c.; Rigault, S.; Bernardinelli, G.; Biinzli, J.-c. G.; Hopfgartner, G. J. Chern. Soc., Dalton Trans. 2000, 3999. 57. Schalley, C. A.; Lutzen, A.; Albrecht, M. Chern. Eur. J. 2004,10, 1072. 58. Albrecht, M. Chern. Rev. 2001, 101,3457-3497. 59. Fujita, M. Structure & Bonding 2000,96, 177. 60. Johnson, D. W.; Xu, J.; Saalfrank, R W.; Raymond, K. N. Angew. Chern. Int. Ed 1999, 38, 2882. 262 61. Telfer, S. G.; Yang, X.-J.; Williams, A. F. J. Chem. Soc., Dalton Trans. 2004, 699. 62. Paul, R L.; Bell, Z. R; Fleming, 1. S.; Jeffery, 1. c.; McCleverty, 1. A.; Ward, M. D. Heteroatom Chemistry 2002,13,567. 63. Saalfrank, R W.; Bernt, I.; Hampel, F. Chem. Eur. J. 2001, 7,2770. 64. SAINT, S. A. D. I. P., Bruker AXS, Inc., Madison, 1995. 65. G. M. She1drick, B. A., Inc., WI, USA, 1996, Xprep 66. G. M. She1drick, B. A., Inc., WI, USA, 1996, SADABS. 67. G. M. She1drick, S., Bruker AXS, Inc., WI, USA, 1997 SHELXTL.