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-{radical dot}3, p-H-C6F4OCH-{radical dot}3 and p-(CH3)2-C6F-{radical dot}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.
Original language | English |
---|---|
Pages (from-to) | 463-471 |
Number of pages | 9 |
Journal | Chemical Physics |
Volume | 112 |
Issue number | 3 |
DOIs | |
State | Published - 15 Mar 1987 |
Externally published | Yes |