Electropolymerization and properties of 3,4-ethylenedioxythiophene backbone polymer with tetrathiafulvalene as pendant

Three 3,4-ethylenedioxythiophene (EDOT) derivatives, including an EDOT-tetrathiafulvalene (TTF) derivative, were synthesized by Steglich esterification of carboxylic acids with hydroxymethyl EDOT (3,4-ethylenedioxythiophene methanol). The UV spectra showed that there was no distinctive intramolecular interaction for the EDOT–TTF monomer between the EDOT and the TTF moieties in the ground state; however, the cyclic voltammetry responses implied that such intramolecular interaction occurred. Electropolymerization in excessive potential could bring in strong overoxidation effects and degradation in the polymer film. The polymers were simulated using density functional theory with Gaussian03 package and the optimized HOMO and LUMO state were figured out. The conductivity of TTF-polymer was 6 S·cm⁻¹ obtained by galvano station and 4.8 × 10⁻³ S·cm⁻¹ obtained by potentiostatic electropolymerization after doping with 7,7,8,8-tetracyanoquinodimethane. The results indicated that this polymer was a reasonable candidate for conducting materials and it was meaningful to increase the conductive dimensions of TTF polymers by chemical doping. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013