Electrochemical materials science: calculation vs. experiment as predictive tools in tailoring intrinsically conducting polythiophenes

Abstract

A series of 3-(p-X-phenyl)thiophene monomers (X = −H, –CH3, –OCH3, –COCH3, –COOC2H5, –NO2) was electrochemically polymerized to furnish polymer films that could be reversibly reduced and oxidized (n- and p-doped). The oxidation potentials of the monomers and formal potentials of the n- and p-doping processes of polymers were correlated with resonance and inductive effects of the substituents on the phenyl ring as well as the ionization potentials of the monomers calculated via density function theory, which correspond to the energies for generating radical cations during oxidative processes.