SOLUBLE AND STABLE S-HETEROCYCLIC QUINODIMETHANES AND MACROCYCLES

Abstract

Acene-based materials have shown promising applications as semiconductors and chromophores, but acenes longer than pentacene are highly reactive and poorly soluble. In this dissertation, much work has been directed towards the synthesis of stable and soluble acene analogues with extended π conjugation system. We developed a series of linear and V-shaped sulfur-containing, p-quinodimethane embedded acene analogues, it is significant that their dications or tetracations can be regarded as genuine isoelectronic structures of respective acenes or phenes, which was validated by experimental evidence and theoretical calculations. We also utilized this methodology by incorporating sulfur atoms and quinoidal structures into a fully fused macrocycle system, it is worth noting that the designed conjugated macrocycle exhibits global anti-aromatic character. In addition, the macrocycle is demonstrated to have a singlet poly-radical character in the ground state, which may imply an alternative approach to design molecular magnets in the future.