Ruthenium(II)-polypyridyl complexes of similar size but with variable reduction potential undergo efficient photoinduced electron-transfer reactions with phenolate ions in aqueous medium. All these reactions are exergonic and are in accordance with the Marcus theory of electron transfer. At high negative ∆G°Marcus inverted region is observed in this bimolecular photoinduced charge separation reaction.

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The rate constants for the photoinduced electron transfer reactions of Ru(II)-polypyridyl complexes (k q ) with 2,6-disubstituted phenolate ions in aqueous acetonitrile are highly sensitive to change in the (Ru(NN) 3 2`) bulkiness of the ligand in as well as the phenolate ion. The decrease in value with the increase in Ru(NN) 3 2`k q the size of the ligand in and the phenolate ion is ascribed to the decrease in the electronic coupling Ru(NN) 3 2m atrix element, between the donor and acceptor with the increase in the electron transfer distance. The o H DA o, hydrophobic interaction or possible pÈp stacking between the pyridine rings of and the aryl Ru(NN) 3 2m oiety of ArO~leads to less steric e †ect.

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