Solvent and Temperature Dependence of Spin Echo Dephasing for Chromium(V) and Vanadyl Complexes in Glassy Solution

Abstract

The solvent and temperature dependence of the rate constant for spin echo dephasing, 1/Tm, for 0.2 to 1.2 mM glassy solutions of chromyl bis(1-hydroxy-cyclohexanecarboxylic acid), CrO(HCA)−2; aquo vanadyl ion, VO2+(aq), and vanadyl bis(trifluoroacetylacetonate), VO(tfac)2were examined. At low temperatures where 1/T1⪡ 1/Tm, 1/Tmin 1:1 H2O:glycerol is dominated by solvent protons. At low temperature 1/Tmincreases in the order 1:1 H2O:glycerol or 9:1 CF3CH2OH:ethyleneglycol (no methyl groups) < 9:1i-PrOH:MeOH (hindered methyl groups) < 9:1n-PrOH:MeOH (less hindered methyl groups). This solvent dependence of 1/Tmis similar to that observed for nitroxyl radicals, which indicates that the effect of solvent methyl groups on spin-echo dephasing at low temperature is quite general. At higher temperatures the echo dephasing is dominated by spin–lattice relaxation and is concentration dependent. As the glass softens, echo dephasing is dominated by the onset of molecular tumbling.