Voltammetric behavior of poly(vinylferrocene)
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A voltammetric analysis of the electron-transfer process in poly(vinylferrocene) (PVF) has been carried out; the results indicate that the electrochemical behavior of ferrocene and PVF are quite similar. The field effects in the macromolecular environment do, however, appear to influence the microscopic potential for oxidation of adjacent ferrocene residues in PVF. Analysis of the slopes of plots of limiting current versus the square root of the rotation speed indicate that only isolated ferrocene residues in the polymers are oxidized under the conditions of the rotating-disk electrode experiment. Diffusion coefficients were determined experimentally for ferrocene and its macromolecular analogs were quite close to those simply calculated from the Stokes-Einstein relationship. Further, it was demonstrated that the molecular weight, which is inversely proportional to the diffusion coefficient, could be determined by voltammetric techniques.