Jasti, RameshShear, Trevor2021-09-132021-09-132021-09-13https://hdl.handle.net/1794/26658Cyclophanes are a venerable class of macrocyclic and cage compounds that often include unique properties owing to their unusual conformations and high strain. Due to these traits, synthesis of new, complex cyclophanes has remained difficult because of the need for harsh reaction conditions, difficult purification steps, and often resulting in low yields. Utilizing the error-correcting nature of dynamic covalent chemistry in conjunction with the directing ability of self-assembly, thiol-disulfide exchange has been used for the facile synthesis of discrete disulfide, thioether, sulfone, and hydrocarbon cyclophanes using pnictogen-assisted self-assembly. This dissertation expands on this synthetic method and explores its full capability in synthesizing a wide variety of new cyclophanes while using ‘design of experiments’ to quickly and efficiently optimize reaction conditions. Chapter I is a review covering two key synthetic methods required for the formation of discrete disulfide cyclophanes: 1) the self-editing ability of dynamic covalent chemistry which often leads to the most stable thermodynamic products and 2) the use of self-assembly to form complex structures without outside manipulation. In Chapter II, the synthetic tolerance of this method to form disulfide cyclophanes with the presence of reactive functional groups is explored. The utility of ‘design of experiments’ is also demonstrated by considerably increasing the yield of targeted cyclophanes from two different disulfide systems with minimal experimental effort. Chapter III discusses the discovery of a trithioorthoformate capped cage compound and its yield optimization. The utility of this pnictogen-assisted self-assembly method is fully explored in Chapter IV resulting in 21 new disulfide and thioether cyclophanes, ranging from large extended aromatic systems to linear alkene/alkyne to highly twisted heterocyclic spiro compounds. In Chapter V, the current synthetic progress towards disulfide and thioether perylene diimide cyclophane chromophores is discussed. Chapter VI includes conclusions and future directions of the project. This dissertation includes co-authored material and previously published results.en-USAll Rights Reserved.dynamic covalent chemistryself-assemblysupramolecular chemistryElectronic Thesis or Dissertation