Abstract
The ion exchange occurring between a poly(vinylferrocene) (PVF) film and the bathing solution during the oxidation−reduction process was studied by probe beam deflection (PBD) in aqueous and nonaqueous media. In nonaqueous media the results for different electrolyte salts indicate that anions are exchanged. In aqueous media, the ion exchange is strongly affected by the anion present in the solution. In tetrafluoroborate and hexafluorophosphate solutions, cation exchange is observed while in toluenesulfonate solution anion exchange in observed. In perchlorate and trifluoromethanesulfonate solutions a mixed mechanism involving cation and anion exchange is observed. Expulsion of cations precedes anion insertion on oxidation. The ion flux is not affected by the pH (in the range from 1 to 7) or the electrolyte concentration (between 0.1 and 4 M). The kind of ion exchanged appears to correlate with the type of interaction (attractive or repulsive) between redox centers inside the film seen from voltammogram sha...
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