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Temperature effects on electron transfer within intervalence bis(hydrazine) radical cations

Nelsen, Stephen F. and Ismagilov, Rustem F. and Gentile, Kevin E. and Powell, Douglas R. (1999) Temperature effects on electron transfer within intervalence bis(hydrazine) radical cations. Journal of the American Chemical Society, 121 (30). pp. 7108-7114. ISSN 0002-7863. doi:10.1021/ja984047k.

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Analyses of the shape of intervalence charge-transfer bands at various temperatures (255−325 K in most cases) in acetonitrile are reported for the radical cations of bis(2-tert-butyl-2,3-diazabicyclo[2.2.2]oct-3-yl) hydrazines that are bridged by 2,5-xylene-1,4-diyl (2^+), durene-1,4-diyl (3^+), naphthalene-1,4-diyl (4^+), biphenyl-4,4‘-diyl (5^+), and 9,9-dimethylfluorene-2,7-diyl (6^+) aromatic rings. Electron-transfer (ET) rate constants measured by ESR as a function of temperature are reported for 4^+−6^+. Despite the fact that the ET barriers for these compounds are dominated by vibrational reorganization, explicit inclusion of vibronic coupling effects is not necessary for the prediction of their ET rate constants from the optical spectra. Rate constants in excellent agreement with the measured ones are predicted by a classical analysis of charge-transfer band shape, if the diabatic surfaces are changed from the usual assumption that they are parabolas to ones that fit the shape of the charge-transfer bands.

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Ismagilov, Rustem F.0000-0002-3680-4399
Additional Information:Copyright © 1999 American Chemical Society. Published In Issue: August 04, 1999. Received November 23, 1998. Revised Manuscript Received May 24, 1999. We thank the National Science Foundation for support of this work under grant CHE-9417946, the NSF major instrument program and the University of Wisconsin for funds used in purchase of the diffractometers, spectrometers, and computer equipment used, and the Dow Chemical Company for a fellowship for R.F.I.. We thank Dmitry Matyushov for discussion of temperature coefficients using his solvent theory. Supporting Information Available: Crystallographic data for 5^0, 5^(2+)(SbF_6^-)_2·CH_3CN, 8^+(SbF_6^-)·^(1/2)Et_2O, and 9^+(SbF_6^-), numbered thermal ellipsoid drawings, heavy atom positions, and experimental for preparation of 4, 5, 6, 8, 9, 10, and their radical cations. This material is available free of charge via the Internet at
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University of WisconsinUNSPECIFIED
Dow Chemical CompanyUNSPECIFIED
Subject Keywords:transfer rates; energy relationships; distance dependence; polar liquids; diporphyrins; complexes; systems; units
Issue or Number:30
Record Number:CaltechAUTHORS:20130821-160726623
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:40841
Deposited By: Whitney Barlow
Deposited On:28 Aug 2013 23:08
Last Modified:10 Nov 2021 00:09

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