Title: Intramolecular Electron Transfer in Bis(<i>p</i>-Nitrophenyl) Anions and Its Effect on Electron Spin Resonance Hyperfine Structure
Abstract: The hyperfine structure of electrochemically generated mononegative ion radicals of the type[Complex chemical formula]has been observed, where X=CH2, S, O, CH2CH2, and where X is absent. The hyperfine structure is found to be especially sensitive to the intramolecular electron transfer rate when the latter is the same order of magnitude as the hyperfine intervals when expressed as frequencies. The transfer rate is found to be sensitive to the solvent, and a model is presented that expresses the trapping of the electronic charge by the orientation of solvent dipoles. The mechanism for electron transfer then proceeds through the random motions of the solvent molecules. Hyperfine structures are calculated for a series of transfer rates on the basis of the Anderson—Weiss model for motional narrowing. Good agreement is found between the unusual hyperfine structure observed experimetally and the calculated spectra for certain values of the transfer rate. The shape of the composite two-electron polarographic reduction wave is related to the equilibrium constant for the reaction, S+S==2S—, assuming reversibility of all electron-transfer reactions at the electrodes. Equilibrium constants are reported.
Publication Year: 1963
Publication Date: 1963-08-01
Language: en
Type: article
Indexed In: ['crossref']
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Cited By Count: 113
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