Dynamic polarization of 7Li nuclei in solutions containing radical ions

Dynamic nuclear polarization parameters, obtained at 75 G, are reported for ⁷Li ions in collision with several radical anions and with one radical cation. All systems show large negative ⁷Li N.M.R. enhancements indicative of weak scalar relaxation. However, radical induced relaxation rates derived from ⁷Li T ₁ measurements suggest stronger complexing of lithium ions with radical anions than with the radical cation as would be expected from simple coulombic considerations. Translational modulation of the dipolar interaction best accounts for proton and radical cation dipolar relaxation rates while rotational modulation best accounts for the corresponding radical anion rates; this supports the interpretation above. A model for the lithium radical collision is proposed which implies that, for radical anions, scalar coupling is only apparently weak and that the low ⁷Li scalar relaxation rates observed result from scalar correlation times (τ_c = 10^-8-10^-9 s) longer than any yet observed by this technique. The model predicts that, for certain ranges of τ_c, increasing strength of complex formation should lead to smaller scalar relaxation rates and more negative enhancements, in contrast with the behaviour of fluorocarbons where the reverse was true. The predicted dependence of enhancement upon τ_c also suggests that ⁷Li enhancements should be extremely sensitive to variations in the chemical properties of the system.