Main group supramolecular coordination chemistry: Design strategies and dynamic assemblies

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Title: Main group supramolecular coordination chemistry: Design strategies and dynamic assemblies
Author: Pitt, Melanie A., 1980-
Abstract: Main group supramolecular chemistry is a rapidly expanding field that combines the tools of coordination chemistry with the unusual and frequently unexpected coordination preferences exhibited by the main group elements. Application of established supramolecular design principles to those elements provides access to novel structure types and the possibility of new functionality introduced by the rich chemistry of the main group. Chapter I is a general review of the field of main group supramolecular chemistry, focusing in particular on the aspects of coordination chemistry and rational design strategies that have been thus far used to prepare polynuclear "metal"-ligand assemblies. Chapter II is a discussion of work toward supramolecular assemblies based on the coordination preferences of lead(II), in particular focusing on the 2-mercaptoacetamide and arylthiolate functionalities to target four-coordinate and three-coordinate geometries, respectively. Several possible avenues for further pursuing this research are suggested, with designs for ligands that may provide a more fruitful approach to the coordination of lead(II). Chapter III deals with the preparation of As 2 L 3 assemblies based on flexible ligand scaffolds. These assemblies exhibit structural changes in response to temperature and solvent, which may provide some insight into the subtle shape requirements involved in supramolecular guest binding. Chapter IV continues this work with an examination of how ligand structure affects mechanical coupling of stereochemistry between metal centers when the chelate ring is completed by a secondary bonding interaction such as the As-π contact. Finally, Chapter V presents a crystallographic and synthetic study of the nature of the interaction between pnictogens and arene rings. This interaction is ubiquitous in the coordination chemistry performed in the Johnson laboratory; understanding the role these interactions play in determining the final structure of supramolecular assemblies is vital to the preparation of more complex structures. Chapter VI presents a set of conclusions and outlook for future work on lead(II) supramolecular assemblies and the dynamic assemblies prepared from flexible organic scaffolds. This dissertation contains previously published and coauthored material.
Description: xxi, 172 p. : ill. (some col.) A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number.
Date: 2009-06

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