The driving force dependence for the photoinduced electron transfer (ET) from ∗Ru(phen)32+ (phen = 1.10-phenanthroline) to several cationic M(phen)3″+ complexes (MCo, Ni, Rh, Cr; n = 2, 3) has been measured in water and in the presence of polyanionic microheterogeneous environments. The anionic host utilized in this study are poly(styrenesulfonate) (PSS) and calf-thymus DNA. In water the driving force dependence of the observed rates, plot of log(kq) versus ΔG (Marcus plot), reaches a plateau corresponding to the rate of diffusion of the reactants. Qualitatively, the Marcus plot is shallower in the case of PSS compared to that measured in DNA and water. This behavior is explained in terms of differences in bimolecular ET kinetics between the DNA and PSS systems.
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Turró et al. (1996) studied this question.
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