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

doi:10.1021/jp511213p

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 journal › Article › peer-review

10 Scopus citations

Abstract

Transient absorption decay rate constants (k_obs) for reactions of electronically excited zinc tetraphenylporphyrin (³ZnTPP) with triruthenium oxo-centered acetate-bridged clusters [Ru₃(μ₃-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, k_q, for ³ZnTPP/1-3 are 3.0 × 10⁹, 1.5 × 10 ⁹, and 1.1 × 10⁹ M^-1 s^-1, respectively). Values of k_q for reactions of ³ZnTPP∗ with 1-3 and Ru₃(μ₃-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 language	English (US)
Pages (from-to)	7473-7479
Number of pages	7
Journal	Journal of Physical Chemistry B
Volume	119
Issue number	24
DOIs	https://doi.org/10.1021/jp511213p
State	Published - Jun 18 2015

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Surfaces, Coatings and Films
Materials Chemistry

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@article{007a9050a6004cb48d6810680a3b3c05,

title = "Electron-Transfer Reactions of Electronically Excited Zinc Tetraphenylporphyrin with Multinuclear Ruthenium Complexes",

abstract = "Transient absorption decay rate constants (kobs) for reactions of electronically excited zinc tetraphenylporphyrin (3ZnTPP) with triruthenium oxo-centered acetate-bridged clusters [Ru3(μ3-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 Ru3(μ3-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.",

author = "Jane Henderson and Glover, \{Starla D.\} and Lear, \{Benjamin J.\} and Don Walker and Winkler, \{Jay R.\} and Gray, \{Harry B.\} and Kubiak, \{Clifford P.\}",

note = "Publisher Copyright: {\textcopyright} 2014 American Chemical Society.",

year = "2015",

month = jun,

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doi = "10.1021/jp511213p",

language = "English (US)",

volume = "119",

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journal = "Journal of Physical Chemistry B",

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T1 - Electron-Transfer Reactions of Electronically Excited Zinc Tetraphenylporphyrin with Multinuclear Ruthenium Complexes

AU - Henderson, Jane

AU - Glover, Starla D.

AU - Lear, Benjamin J.

AU - Walker, Don

AU - Winkler, Jay R.

AU - Gray, Harry B.

AU - Kubiak, Clifford P.

PY - 2015/6/18

Y1 - 2015/6/18

N2 - Transient absorption decay rate constants (kobs) for reactions of electronically excited zinc tetraphenylporphyrin (3ZnTPP) with triruthenium oxo-centered acetate-bridged clusters [Ru3(μ3-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 Ru3(μ3-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.

AB - Transient absorption decay rate constants (kobs) for reactions of electronically excited zinc tetraphenylporphyrin (3ZnTPP) with triruthenium oxo-centered acetate-bridged clusters [Ru3(μ3-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 Ru3(μ3-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.

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ER -

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

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