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J Phys Chem B. 2013 Jan 10;117(1):426-32. doi: 10.1021/jp3099945. Epub 2012 Dec 19.

Hole mobility in porphyrin- and porphyrin-fullerene electropolymers.

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Department of Chemistry and Biochemistry, Center for Bioenergy and Photosynthesis, Arizona State University, Tempe, Arizona 85287, United States.


Charge transport within films of several new types of electropolymerized porphyrin and porphyrin-fullerene dyad polymers was studied in order to obtain information on the suitability of these organic semiconductors for applications in solar energy conversion, sensor devices, etc. The films, prepared by electropolymerization on a conductive substrate, were immersed in acetonitrile and studied using chronocoulometric and cyclic voltammetric electrochemical methods. The charge diffusion coefficients were found to be dependent upon the electrolytic medium. Electrolyte anion size plays a significant role in determining the rate of migration of charge through the polymers, demonstrating that migration of positive charge is accompanied by migration of negative counterions. Bulkier anions markedly decrease the charge diffusion coefficient. This strong dependence suggests that anion mobility is the rate-limiting process for diffusional charge transport within the porphyrin polymer films and that the largest rates obtained are lower limits to the intrinsic cation mobility. With electrolytes containing the relatively small perchlorate anion, charge diffusion coefficients of the porphyrin polymers were similar to those reported for polyaniline under acidic conditions. The charge diffusion coefficient for a zinc porphyrin polymer was found to decrease 2 orders of magnitude in the presence of pyridine, suggesting that metal-containing porphyrins polymer films may have sensor applications. Cation (hole) mobilities previously reported in the literature for porphyrin-containing polymers with chemical structures quite different from those investigated here were much smaller than those found for the polymers in this study, but further investigation suggests that the differences are due to choice of electrode size and material.

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