A Caltech Library Service

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. doi:10.1021/j100071a001.

[img] PDF (Detailed descriptions of the synthesis and characterization of Ma, Mb, and Ir(spacer)py^+ complexes; Figure S 1 illustrating the absorption and luminescence spectra of Ma (4 pages)) - Supplemental Material
See Usage Policy.


Use this Persistent URL to link to this item:


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
Related URLs:
URLURL TypeDescription Information
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
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.
Funding AgencyGrant Number
Department of Energy (DOE)DE-AC02-76CH00016
Department of EducationUNSPECIFIED
Issue or Number:20
Record Number:CaltechAUTHORS:20180529-161428891
Persistent URL:
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
Deposited By: George Porter
Deposited On:30 May 2018 14:52
Last Modified:15 Nov 2021 20:41

Repository Staff Only: item control page