Studies of the inner reorganization energies of the cation radicals of 1,4-bis(dimethylamino)benzene, 9,10-bis(dimethylamino)anthracene, and 3,6-bis(dimethylamino)durene by photoelectron spectroscopy and reinterpretation of the mechanism of the electrochemical oxidation of the parent diamines

The Journal of Physical Chemistry. a
Nadine E GruhnDennis H Evans

Abstract

The inner reorganization energy of the cation radical of 1,4-bis(dimethylamino)benzene, 1, has been determined to be 0.72 +/- 0.02 eV by means of gas-phase photoelectron spectroscopy (PES). PES studies of 9,10-bis(dimethylamino)anthracene, 2, and 3,6-bis(dimethylamino)durene, 3, demonstrate that their reorganization energies are smaller than that of 1. The effect of lowering the inner reorganization energy on the rate constant for an electrochemical electron-transfer reaction is to increase the electron-transfer rate constant, k(s). However, voltammetric studies of the two-electron oxidation of 2 and 3 indicate that the values of k(s) for each step are smaller than those for 1, in contradistinction to the measured differences in reorganization energies. The voltammetric studies of 2 and 3 were reinterpreted according to a mechanism in which each step of oxidation was written as a two-step process, electron transfer with a small inner reorganization energy plus a chemical step of structural change. The agreement of simulations according to this mechanism with the experimental data was excellent. The new reaction scheme eliminated some suspicious features previously obtained with an analysis where electron transfer and structural...Continue Reading

References

Jul 4, 2002·Journal of the American Chemical Society·Nadine E GruhnJean-Luc Brédas
Jul 23, 2004·The Journal of Chemical Physics·M MalagoliJ L Brédas
Nov 26, 2004·Journal of the American Chemical Society·Xenia AmashukeliHarry B Gray

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Citations

Jul 17, 2009·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Ole HammerichJørn B Christensen
May 1, 2007·Chemistry : a European Journal·Norma A Macías-Ruvalcaba, Dennis H Evans
Nov 20, 2016·Chemistry : a European Journal·Masashi UebeAkihiro Ito
Jan 29, 2009·The Journal of Physical Chemistry. B·Carlo BrunoLawrence T Scott
Nov 30, 2006·Langmuir : the ACS Journal of Surfaces and Colloids·Nadine E GruhnDennis H Evans
Sep 7, 2021·Physical Chemistry Chemical Physics : PCCP·Cecilie L AndersenOle Hammerich
Dec 1, 2006·The Journal of Physical Chemistry. B·Norma A Macías-Ruvalcaba, Dennis H Evans
Jan 26, 2007·The Journal of Organic Chemistry·Christian A ChristensenMartin R Bryce

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