Electrochemical, Conductive, and Magnetic Properties of 2,7-Carbazole-Based Conjugated Polymers

Novel poly(2,7-carbazole)s (i.e., poly( N -octyl-2,7-carbazolediyl) and poly( N -(4-hexylbenzoyl)-2,7-carbazolediyl)) and their alternating thiophene, bithiophene, and 3,4-ethylenedioxy-2,5-thienylene copolymers have been investigated by cyclic voltammetry, UV−vis spectroelectrochemistry, electrochemical quartz crystal microbalance, in-situ electron spin resonance, and in-situ conductivity techniques. All polymer films undergo reversible oxidation and partially reversible reduction processes. In poly( N -octyl-2,7-carbazolediyl), two isoelectronic oxidation processes produce radical cations and dications with charge localization at the carbazole subunits. The presence of a strong electron-withdrawing substituent onto the nitrogen atom in the homopolymer leads to an increase by 3 orders of magnitude of the conductivity (i.e., 1 × 10 -2 S/cm). Similarly, in alternating copolymers, the oxidative charge is more delocalized over the polyconjugated backbone with in-situ conductivities in the range of 4 × 10 -2 −4 × 10 -3 S/cm.