Electron-Transfer Reactions of Electronically Excited Zinc Tetraphenylporphyrin with Multinuclear Ruthenium Complexes

Abstract

Transient absorption decay rate constants (k_(obs)) for reactions of electronically excited zinc tetraphenylporphyrin (^3ZnTPP*) with triruthenium oxo-centered acetate-bridged clusters [Ru_3(μ_3-O)(μ-CH_3CO_2)_6(CO)(L)]_2(μ-pz), where pz = pyrazine and L = 4-cyanopyridine (cpy) (1), pyridine (py) (2), or 4-dimethylaminopyridine (dmap) (3), were obtained from nanosecond flash-quench spectroscopic data (quenching constants, k_q, for ^3ZnTPP*/1–3 are 3.0 × 10^9, 1.5 × 10^9, and 1.1 × 10^9 M^(–1) s^(–1), respectively). Values of k_q for reactions of ^3ZnTPP* with 1–3 and Ru_3(μ_3-O)(μ-CH_3CO_2)_6(CO)(L)_2 [L = cpy (4), py (5), dmap (6)] monomeric analogues suggest that photoinduced electron transfer is the main pathway of excited-state decay; this mechanistic proposal is consistent with results from a photolysis control experiment, where growth of characteristic near-IR absorption bands attributable to reduced (mixed-valence) Ru_3O-cluster products were observed.

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