Abstract
A comparative E.S.R. study of the potassium salts of the anion radicals of tetracyanoquinodimethan(TCNQ) and tetrafluorotetracyanoquinodimethan(TCNQF4) in dilute solutions of ether type solvents reveals that both anion radicals are ion paired. Careful measurements of the hyperfine splittings (hfs) as a function of temperature for both anions in solution show that the isotropic hfs are temperature and solvent dependent. Generally, at temperatures below room temperature, both anion radicals in solution display linewidth alternation phenomena which arise from modulation of the nitrogen and fluorine hfs in TCNQ and TCNQF4, respectively. In contrast, the isotropic g-values of both anion radicals in solution are independent of temperature and the solvents used in this study. The experimental evidence, molecular orbital calculations of the charge density distribution in the free anion radicals, calculations of the ion pair association energies for various K+/TCNQ- and K+/TCNQF4 structures and comparison of the c...
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