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Photoinduced Electron Transfer in Iridium(spacer)pyridinium Complexes

Farid, Ramy S. and Chang, I-Jy and Winkler, Jay R. and Gray, Harry B. (1994) Photoinduced Electron Transfer in Iridium(spacer)pyridinium Complexes. Journal of Physical Chemistry, 98 (20). pp. 5176-5179. ISSN 0022-3654 . http://resolver.caltech.edu/CaltechAUTHORS:20180529-161428891

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Abstract

Photoinduced electron-transfer (ET) reactions in a series of iridium(spacer)pyridinium complexes, [Ir(µ-pz*)-(CO)Ph_2POC_6H_4(CH_2)_n-A^+]_2 (pz* = 3,5-dimethylpyrazolyI; Ph = C_6H_5; C_6H_4 = phenylene; A^+ = pyridinium (py^+) or substituted py^+; n = 0-3), have been studied in acetonitrile solution at room temperature. The rates of singlet (^1Irz* → A^+: ^1ET) reactions were determined for each complex, and for n = 1 and 2 species, the rates of thermal charge recombination (ET^b) also were measured. The ET rates for the n = 1 system display a Gaussian free-energy dependence ( λ = 1.0 eV, H_(AB) = 5 cm^(-1)). With one exception, maximum ET rates exhibit an exponential dependence upon the number of carbon atoms (α_c) in the spacer. The exception is the n = 1 (α_c = 5) system; k_(max) is almost a factor of 100 slower than predicted by the exponential dependence on α_c, indicating that donor-acceptor electronic coupling through a single methylene link is unusually weak.


Item Type:Article
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https://dx.doi.org/10.1021/j100071a001DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/j100071a001PublisherSupporting Information
ORCID:
AuthorORCID
Winkler, Jay R.0000-0002-4453-9716
Additional Information:© 1994 American Chemical Society. Received: December 17, 1993; In Final Form: March 30, 1994. Research at the California Institute of Technology was supported by NSF Grants CHE-8922067 and CHE-9311587. Research carried out at Brookhaven National Laboratory was under contract DE-AC02-76CH00016 with the US. Department of Energy and supported by its Division of Chemical Sciences, Office of Basic Research. R.S.F. thanks the US. Department of Education for a graduate fellowship.
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Funding AgencyGrant Number
NSFCHE-8922067
NSFCHE-9311587
Department of Energy (DOE)DE-AC02-76CH00016
Department of EducationUNSPECIFIED
Record Number:CaltechAUTHORS:20180529-161428891
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20180529-161428891
Official Citation:Photoinduced Electron Transfer in Iridium(spacer)pyridinium Complexes Ramy S. Farid, I-Jy Chang, Jay R. Winkler, and Harry B. Gray The Journal of Physical Chemistry 1994 98 (20), 5176-5179 DOI: 10.1021/j100071a001
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86693
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:30 May 2018 14:52
Last Modified:30 May 2018 14:52

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