Synthesis and radical coupling of pyridine-bridged π-extended tetrathiafulvalene (TTF)-type donors and push–pull analogues

Abstract

A new family of π-extended TTF analogues (3a–c) and D–π–A chromophores (5a–c), in which the electroactive units (1,3-dithiole rings and 2,2-dicyanovinyl groups) are connected through a pyridine bridge with a meta substitution pattern, is reported. The redox behavior of these compounds has been investigated by cyclic voltammetry and theoretical calculations performed at the B3P86/6-31G** level. Unlike many π-extended TTF derivatives, the 1,3-dithiole rings in compounds 3a–c do not behave independently and two oxidation processes are observed with an anodic separation ranging from 50 to 150 mV. Calculations show that electrons are equally extracted from both dithiole rings. A biradical structure is predicted for the dication state due to the near-degeneracy of the HOMO and HOMO − 1 orbitals. The presence of both donor (D) and acceptor (A) fragments in conjugates 5 results in irreversible oxidation and reduction processes associated with the 1,3-dithiole ring and with the 2,2-dicyanovinyl moiety, respectively. An electrochemical–chemical–electrochemical (ECE) process takes place for all the compounds reported. The chemical process implies the dimerization of the radical cation for compounds 5 and the oligomerization of the biradical dication for compounds 3. The ECE process therefore generates new neutral dimeric (5) or oligomeric (3) species that incorporate the TTF vinylogue core.