Electrochemical characterisation of polyvinylferrocene polymers: substituent effects on the redox reaction

Abstract

The electrochemical behaviour of substituted ferrocene monomers and polymers was investigated using the techniques of cyclic voltammetry and pulse voltammetry at a platinum electrode. Both monomers and polymers obeyed the Hammett linear free-energy relationship between the half-wave potentials, E_1/2, and the σ constants of the substituents. Normal pulse-voltammetric studies indicate that nearly all the ferrocene residues in the polymer are accessible to electron transfer in the electrode reaction. Diffusion coefficients calculated for substituted ferrocene polymers were in good agreement with those calculated using theoretical treatments.