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Gaussian Free-Energy Dependence of Electron-Transfer Rates in Iridium Complexes

Fox, Lucius S. and Kozik, Mariusz and Winkler, Jay R. and Gray, Harry B. (1990) Gaussian Free-Energy Dependence of Electron-Transfer Rates in Iridium Complexes. Science, 247 (4946). pp. 1069-1071. ISSN 0036-8075. doi:10.1126/science.247.4946.1069.

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The kinetics of photoinduced electron-transfer (ET) reactions have been measured in a series of synthetic donor-acceptor complexes. The electron donors are singlet or triplet excited iridium(I) dimers (Ir_2), and the acceptors are N-alkylpyridinium groups covalently bound to phosphinite ligands on the Ir_2 core. Rate constants for excited-state ET range from 3.5 x 10^6 to 1.1 x 10^(11) per second, and thermal back ET (pyridinium radical to Ir_(2)^+) rates vary from 2.0 x 10^(10) to 6.7 x 10^7 per second. The variation of these rates with driving force is in remarkably good agreement with the Marcus theory prediction of a Gaussian free-energy dependence.

Item Type:Article
Related URLs:
URLURL TypeDescription JSTORArticle
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 1990 American Association for the Advancement of Science. 7 September 1989; accepted 4 December 1989. We thank B. S. Brunschwig for assistance with the λ_OUT calculation. The work of L.S.F.w as supported by a graduate research fellowship from British Petroleum America. Research at the California Institute of Technology was supported by National Science Foundation grant CHE84-19828 (contribution 7977 from the Arthur Amos Noyes Laboratory). Research at Brookhaven National Laboratory was carried out under contract DE-AC02-76CH00016 with the U.S. Department of Energy and supported by its Division of Chemical Sciences, Office of Basic Energy Sciences.
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British Petroleum AmericaUNSPECIFIED
Department of Energy (DOE)DE-AC02-76CH00016
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Arthur Amos Noyes Laboratory7977
Issue or Number:4946
Record Number:CaltechAUTHORS:20150126-094014828
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Official Citation:Fox, L. S., Kozik, M., Winkler, J. R., & Gray, H. B. (1990). Gaussian Free-Energy Dependence of Electron-Transfer Rates in Iridium Complexes. Science, 247(4946), 1069-1071. doi: 10.1126/science.247.4946.1069
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:54066
Deposited By: Jason Perez
Deposited On:26 Jan 2015 20:25
Last Modified:10 Nov 2021 20:28

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