Abstract
ESR studies of ion pair complexes formed in benzene between valinomycin (VM) and the alkali metal salts of tetracyanoethylene (MTCNE) are reported. The absolute value of the alkali metal hyperfine splitting constants for the ion pair complexes are given for the temperature range 10 to 70°C. The VMNa +-TCNE − complex has a temperature dependent structure while the VMK +-TCNE − and VMCs +-TCNE − complexes exist in only one structural form. The formation of a VMNH 4 +-TCNE − complex is reported and evidence is presented to show that VM exhibits anion selectivity as well as cation selectivity in the formation of VM ion pair complexes in low dielectric media. Pulse ESR studies of longitudinal and transverse relaxation times for the VMK +-TCNE −complex at room temperature give T 1 = 3.8 ± 0.1 μsec and T 2 = 2.2 μsec. The value obtained for T 2 by pulse ESR is confirmed by computer simulations of the VMK +-TCNE − spectrum. The T 2 values observed are taken as evidence that aggregation of VMM +-TCNE − complexes is not significant at low complex concentrations.
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