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

Jane Henderson, Starla D. Glover, Benjamin J. Lear, Don Walker, Jay R. Winkler, Harry B. Gray, Clifford P. Kubiak

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

Transient absorption decay rate constants (kobs) for reactions of electronically excited zinc tetraphenylporphyrin (3ZnTPP) with triruthenium oxo-centered acetate-bridged clusters [Ru33-O)(μ-CH3CO2)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, kq, for 3ZnTPP/1-3 are 3.0 × 109, 1.5 × 10 9, and 1.1 × 109 M-1 s-1, respectively). Values of kq for reactions of 3ZnTPP∗ with 1-3 and Ru33-O)(μ-CH3CO2)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) Ru3O-cluster products were observed.

Original languageEnglish (US)
Pages (from-to)7473-7479
Number of pages7
JournalJournal of Physical Chemistry B
Volume119
Issue number24
DOIs
StatePublished - Jun 18 2015

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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