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Electron Tunneling through Water: Oxidative Quenching of Electronically Excited Ru(tpy)_2^(2+)(tpy = 2,2‘:6,2‘ ‘-terpyridine) by Ferric Ions in Aqueous Glasses at 77 K

Ponce, Adrian and Gray, Harry B. and Winkler, Jay R. (2000) Electron Tunneling through Water: Oxidative Quenching of Electronically Excited Ru(tpy)_2^(2+)(tpy = 2,2‘:6,2‘ ‘-terpyridine) by Ferric Ions in Aqueous Glasses at 77 K. Journal of the American Chemical Society, 122 (34). pp. 8187-8191. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20170321-101627546

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Abstract

The luminescence lifetime of Ru(tpy)_2^(2+) (tpy = 2,2‘:6,2‘ ‘-terpyridine) is 8.0 μs in H_2SO_4/H_2O and HSO_3F/H_2O glasses (25% v/v) at 77 K, and 10.2 μs in D_2SO_4/D_2O (25% v/v). Addition of moderate concentrations of the powerfully oxidizing Fe(OH_2)_6^(3+) ion to the glasses leads to accelerated and highly nonexponential *Ru(tpy)_2^(2+) decay kinetics. The quenching is attributed to electron transfer from *Ru(tpy)_2^(2+) to randomly dispersed Fe(OH_2)_6^(3+) complexes. The luminescence decay kinetics and quantum yields in the three aqueous glasses indicate that the electron-transfer rate constants decrease from ∼10^(13) s^(-1) at van der Waals contact with an exponential distance decay constant of 1.68 ± 0.07 Å^(-1).


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja000017hDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja000017hPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja000017hPublisherSupporting Information
ORCID:
AuthorORCID
Gray, Harry B.0000-0002-7937-7876
Winkler, Jay R.0000-0002-4453-9716
Additional Information:© 2000 American Chemical Society. Received January 3, 2000. Publication Date (Web): August 8, 2000. We thank D. N. Beratan, R. J. Cave, N. S. Lewis, R. A. Marcus, J. R. Miller, and M. D. Newton for helpful discussions. This research was supported by NSF Grant CHE9610164 and the Arnold and Mabel Beckman Foundation.
Funders:
Funding AgencyGrant Number
NSFCHE-9610164
Arnold and Mabel Beckman FoundationUNSPECIFIED
Issue or Number:34
Record Number:CaltechAUTHORS:20170321-101627546
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170321-101627546
Official Citation:Electron Tunneling through Water:  Oxidative Quenching of Electronically Excited Ru(tpy)22+ (tpy = 2,2‘:6,2‘ ‘-terpyridine) by Ferric Ions in Aqueous Glasses at 77 K Adrian Ponce, Harry B. Gray, and Jay R. Winkler Journal of the American Chemical Society 2000 122 (34), 8187-8191 DOI: 10.1021/ja000017h
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:75270
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:21 Mar 2017 17:34
Last Modified:22 Nov 2019 09:58

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