The hfi parameters and structure of radical-anions of substituted tetra- and pentafluorobenzenes. Theory and experiment (OD ESR) |
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Affiliation: | 1. Division of Intensive Care Unit, Nippon Medical School Chiba Hokusoh Hospital, Chiba, Japan;2. Department of Cardiovascular Medicine, Nippon Medical School, Tokyo, Japan |
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Abstract: | Optically detected electron spin resonance (OD ESR) of radical pairs has been employed to take ESR spectra of short-lived radical-anions of substituted fluorobenzenes in liquid non-polar solutions at nearly room temperatures. The quantum-chemical hfi analysis has taken into account possible manifestations of pseudo-Jahn—Teller effects. As shown by comparison with experiment,C6F5OCH−3, p-H-C6F4OCH−3 and p-(CH3)2-C6F−4 are pseudo-π-radicals with non-planar distortions. A peculiar feature of these radicals is that their structure corresponds to the Jahn—Teller stabilization of excited Π* states. The effect results from a stronger interaction of the Σ* state with Π* than with the ground Π state, because the SOMO space localizations coincide in the Σ* and Π* states. |
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