Abstract
The reactivity of the cation radicals formed by oxidation of four 3,4-alkylenedioxypyrrole and 3,4-alkylenedioxythiophene monomers has been investigated by fast scan cyclic voltammetry, from the V/s to the kV/s range. The results show that all cation radicals react quickly as desired for electropolymerization and electroactive polymer film formation on platinum and glassy carbon electrodes, despite the strong donating effect of the O-alkyl substituents. Surprisingly, the chemical reversibility of the cation radical formation and subsequent neutralization is easily observed on gold, due to a strong adsorption phenomenon, which greatly enhances the lifetime of the electrogenerated cation radical and reduces its formation potential. Surface coverage and electronic transfer coefficient measurements comparing the dioxypyrrole and dioxythiophene derivatives suggest a difference in how the adsorbed molecules orient relative to the electrode surface.
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