Published March 2, 1990
| public
Journal Article
Gaussian Free-Energy Dependence of Electron-Transfer Rates in Iridium Complexes
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.
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.Additional details
- Eprint ID
- 54066
- DOI
- 10.1126/science.247.4946.1069
- Resolver ID
- CaltechAUTHORS:20150126-094014828
- British Petroleum America
- CHE84-1982
- NSF
- DE-AC02-76CH00016
- Department of Energy (DOE)
- Created
-
2015-01-26Created from EPrint's datestamp field
- Updated
-
2021-11-10Created from EPrint's last_modified field
- Other Numbering System Name
- Arthur Amos Noyes Laboratory
- Other Numbering System Identifier
- 7977