Abstract
Quenching reactions of the phosphorescent state of Ru(bpydc)34- by a cationic ion, Co(bpy)33+, Co(phen)33+, Co(tpy)23+, and methyl viologen (MV2+) to yield ET products were examined for the aqueous solutions by means of transient absorption kinetic spectroscopy and time-correlated single photon counting technique. A molecular complex formed in the ground state, [Ru(bpydc)34-... Co(tpy)23+], produces ET-products in the bulk with a small fraction of 0.3 on the photoexcitation. The fractions of ET product formation in the collisional quenching by Co(tpy)23+ (0.43) is lower than the re-dissociation fraction (0.71) of an encounter complex, Ru(bpydc)33-−Co(tpy)22+, for the reverse ET reaction. A process to reduce the formation of a cage-complex of [Ru(bpydc)33-...Co(tpy)22+], in the collisional quenching is the conversion of unrelaxed cage-complex to the original reactant pair, [Ru(bpydc)34-...Co(tpy)23+] via a potential intersect between the potential energy surfaces (PES) (avoid crossing). Such rapid a deacti...
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