Association of Electroactive Counterions with Polyelectrolytes. 4. CoordinativeBinding of Ru(edta) to Poly(4-vinylpyridine)

摘要

Previous studies in this series have involved water-soluble polyelectrolytesbased on a polysiloxane or polystyrenesulfonate. The present study employs protonated poly(4-vinylpyridine) (PVP) as the water-soluble cationic polyelectrolyte and Ru(111)(edta)OH2(-) and Ru(11)(edta)OH2 (edta = ethylenediaminetetraacetate) as electroactive counterions. The issues we wanted to consider included the possible competition between coordination and electrostatic association of the counterions with the pyridine or with the pyridinium sites, respectively, the effect of varying the proportions of protonated and unprotonated pyridine groups on the diffusional rates of the PVP-counterion complexes, and the effects of electron transfer between bound and unbound counterions on their measured diffusion coefficients.