A MARY study of radical anions of fluorinated benzenes

Abstract

The paper reports the results of two studies centred on the properties of radical anions of polyfluorinated benzenes in liquid dodecane solutions at room temperature using level crossing (MARY) spectroscopy of spin-correlated radical ion pairs generated in nonpolar solutions by ionizing radiation. The first study takes advantage of the large, nearly two orders of magnitude, span of hyperfine couplings in the series of otherwise similar radical anions to probe into the peculiarities of degenerate electron exchange reaction for system with large hyperfine couplings. The second study provided the first observation of radical anion of 1,3,5-trifluorobenzene and yielded a hyperfine coupling constant of 7.2–7.5 mT with three equivalent fluorine nuclei and coherent lifetime of the radical anion about 20 ns at room temperature, which has thus far precluded its observation by other techniques.