Electrochemical synthesis and characterization of the electronic structure of new conjugated polymers from dithienylene vinylene derivatives

Highly conjugated thiophene derivatives, based on thienylene vinylene and thienylene vinylene phenylene units, have been synthesized in order to examine: (i) the effect of such regular conjugated monomer structures on polymer formation; and (ii) the optical and electrochemical properties of the corresponding macromolecules. The all-trans monomers have been prepared by a Wittig reaction. The polymers have then been synthesized electrochemically. The polymers are electrochromic and can be reversibly doped both oxidatively and reductively. Their electrochemical behavior and optical properties have been analyzed on the basis of a series of quantum-chemical calculations.