Synthesis and characterization of thiophenes locked into an annulene scaffold
O'Connor, Matthew John, 1980-
MetadataShow full item record
O'Connor, Matthew John, 1980-
Highly conjugated carbon-rich systems have demonstrated many attractive applications for fundamental and materials science applications, including--but not limited to--probes for aromaticity, charge-transfer complexes, conducting/semi-conducting materials, linear/nonlinear optical materials, and solar cells. The bulk of this research has focused on carbon-rich fullerenes, conjugated polymers, or polycyclic aromatic hydrocarbons; however, with recent developments in cross-coupling chemistry, carbon rich chemistry, particularly dehydrobenzo[ n ]annulenes (DBAs), has grown to yield molecules of great diversity and utility. Concurrently, materials based on conjugated heterocycles have been developed and display similar and often enhanced properties to the aforementioned carbon rich systems. The lone pair of the heterocycle often adds additional stability and polarizablity, creating novel and tunable molecules. Assimilating techniques used to produce DBAs with heteroaromatic molecules, our work has afforded a novel class of conjugated macrocycles with the highly tunable optical-electronic properties of a DBA system. That in turn has led to the systematic study of the diverse structure-property relationships of the thiophene/DBA hybrids reported herein. Chapter I details the synthetic advances in the field of DBA chemistry. The first section discusses the methods of synthesis, inter- vs. intra- molecular approaches, while the remaining sections provide current examples of the DBAs reported. Chapter II briefly discuses conjugated thiophene chemistry, then describes the advantages of utilizing planarized thiophenes. Several examples of thiophene macrocycles are reviewed: both planar and nonplanar. Particular attention in the review focuses on synthesis, optical properties, and some redox properties. Chapters III and IV detail the synthesis and analysis of thiophenes locked into - and annulene scaffolds, respectively. The dehydrothienoannulenes (DTAs) and DTA/DBA hybrids of chapter III serve as aromatic probes and show significant tunabilty with respect to the number and orientation of the thiophenes. Chapter IV's dehydrobenzoannulenes, which are comprised of a cross-conjugated system, also display a structure-property relationship where the optical properties encompass a wider dispersion of wavelengths. Chapter IV also explores the incorporation of pyridines and the affects on conjugation. The electronic properties of the macrocycles were explored using NMR, UV-Vis absorption and fluorescence spectroscopy, and electrochemically (cyclic voltammetry). Chapter V is devoted to further functionalization of DTAs through alkylation and further cycliziation to yield planarized terthiophene units. This dissertation includes my previously published and co-authored material.