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

Henderson, Jane and Glover, Starla D. and Lear, Benjamin J. and Walker, Don and Winkler, Jay R. and Gray, Harry B. and Kubiak, Clifford P. (2015) Electron-Transfer Reactions of Electronically Excited Zinc Tetraphenylporphyrin with Multinuclear Ruthenium Complexes. Journal of Physical Chemistry B, 119 (24). pp. 7473-7479. ISSN 1520-6106. doi:10.1021/jp511213p. https://resolver.caltech.edu/CaltechAUTHORS:20150804-154353645

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jp511213pDOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp511213pPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jp511213pPublisherSupporting Information
ORCID:
AuthorORCID
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
Kubiak, Clifford P.0000-0003-2186-488X
Additional Information:© 2014 American Chemical Society. Received: November 9, 2014; Revised: December 11, 2014; Published: December 14, 2014. We thank Jonas Petersson for his valuable collaboration. We also thank Professor Judy Kim for use of the Nd:YAG laser, Ignacio López-Peña for his spectroscopic support, and Dr. Brian Leigh for his continual enthusiasm. This work was supported by the National Science Foundation under Grants CHE-1145893 (C.P.K.) and CHE-1305124 (J.R.W., H.B.G.). The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NSFCHE-1145893
NSFCHE-1305124
Issue or Number:24
DOI:10.1021/jp511213p
Record Number:CaltechAUTHORS:20150804-154353645
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150804-154353645
Official Citation: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, and Clifford P. Kubiak The Journal of Physical Chemistry B 2015 119 (24), 7473-7479 DOI: 10.1021/jp511213p
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59194
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:05 Aug 2015 22:27
Last Modified:10 Nov 2021 22:16

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