Abstract |
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 MarcusHush 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 (c) 2012 John Wiley \& Sons, Ltd. |