Electron transfer within 1,3-dinitrobenzene radical anions: electron hopping or superexchange?
Article first published online: 28 MAY 2012
Copyright © 2012 John Wiley & Sons, Ltd.
Journal of Physical Organic Chemistry
Volume 25, Issue 12, pages 1139–1143, December 2012
How to Cite
2012), Electron transfer within 1,3-dinitrobenzene radical anions: electron hopping or superexchange?, Journal of Physical Organic Chemistry. DOI: 10.1002/poc.3057and (
- Issue published online: 7 JAN 2013
- Article first published online: 28 MAY 2012
- Manuscript Accepted: 2 APR 2012
- Manuscript Revised: 14 MAR 2012
- Manuscript Received: 18 JAN 2012
- organic mixed valence;
- dinitroaromatic radical anions;
- Marcus–Hush theory;
- charge-transfer optical bands;
- intramolecular electron transfer;
- EPR spectroscopy
The intramolecular electron transfer on several 1,3-dinitrobenzene radical anions with different substituents on position 5 was studied by electron paramagnetic resonance and optical spectroscopies in MeCN. The radical anions are all charge-localized mixed valence species, as is common for meta-substituted dinitrobenzenes. Rate constants for the electron transfer reaction were obtained by the Marcus–Hush analysis of the intervalence optical bands assuming quartic-augmented energy surfaces and solvent-controlled dynamics. These calculated rate constants match quite well the experimental ones obtained by simulation of the electron paramagnetic resonance spectra, which rules out bridge-reduced states as intermediates in the reaction path and confirms the superexchange mechanism. Copyright © 2012 John Wiley & Sons, Ltd.