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. https://resolver.caltech.edu/CaltechAUTHORS:20150126-094014828
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Abstract
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.
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| 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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| Issue or Number: | 4946 | ||||||||||||
| DOI: | 10.1126/science.247.4946.1069 | ||||||||||||
| Record Number: | CaltechAUTHORS:20150126-094014828 | ||||||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20150126-094014828 | ||||||||||||
| 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 | ||||||||||||
| Collection: | CaltechAUTHORS | ||||||||||||
| Deposited By: | Jason Perez | ||||||||||||
| Deposited On: | 26 Jan 2015 20:25 | ||||||||||||
| Last Modified: | 10 Nov 2021 20:28 |
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