Thieno[3,2-b]thiophene Incorporated Redox Active 22π and 34π Core-Modified Expanded Isophlorinoids

Abstract

Incorporation of a thieno[3,2-b]thiophene into an isophlorinoid-like framework alters the aromaticity by extending the macrocyclic π-circuit. Their opto-electronic and aromatic properties significantly differ from other 22π and 34π porphyrinoids. Among the three different 34π hexaphyrins, furan based hexaphyrin adopts a non-aromatic ‘figure-of-eight’ conformation. Replacing all the furans either by thiophene or selenophene induces a planar conformation with aromatic characteristics. Spectro-electrochemical studies revealed reversible two-electron ring oxidation to yield their 4nπ dicationic species respectively.