Electrochemical responses from the reduction of RuIII (edta) coordinatedto films of high molecular weight poly(4-vinylpyridine) on pyrolytic graphiteelectrodes were studied as functions of film thickness, temperature, supportingelectrolyte composition, and solvent. Responses at filmed electrodes from metalcomplexes that do not coordinate to the films were also examined. With filmsthicker than ca. 1000Å, the current responses are limited by the rates of molecularmotions within the films. Penetration of counterions, segmental motion ofsections of the polymer chains, and juxtapositioning of pairs of attached metalcomplexes to facilitate intercomplex electron transfer within the film or combinationsof the three are suggested as likely current limiting processes
