Abstract
The quantum efficiencies for formation of free radical ions (Φ sep) following electron transfer quenching of the metal-to-ligand charge transfer (MLCT) excited state of a series of [(diimine)Re I(CO) 3L] + complexes by diaza[2.2.2]octane (DABCO) have been determined. The observed correlation between Φ sep and the driving force for back electron transfer in the contact radical pair ( ΔG BET) is consistent with a Marcus inverted region dependence of the rate of back electron transfer on Δ G BET. Comparison of the data for the present study with that for related systems suggests that: (i) the contact radical ion pair formed by electron transfer quenching has triplet spin multiplicity; (ii) the observed rate of charge recombination in the contact radical ion pair is controlled by the rate of triplet—singlet intersystem crossing.
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