Electron spin relaxation rates for semiquinones between 25 and 295K in glass-forming solvents

Electron spin lattice relaxation rates for five semiquinones (2,5-di-t-butyl-1,4-benzosemiquinone, 2,5-di-t-amyl-1,4-benzosemiquinone, 2,5-di-phenyl-1,4-benzosemiquinone, 2,6-di-t-butyl-1,4-benzosemiquinone, tetrahydroxy-1,4-benzosemiquione) were studied by long-pulse saturation recovery EPR in 1:4 glycerol:ethanol, 1:1 glycerol:ethanol, and triethanolamine between 25 and 295K. Although the dominant process changes with temperature, relaxation rates vary smoothly with temperature, even near the glass transition temperatures, and could be modeled as the sum of contributions that have the temperature dependence that is predicted for the direct, Raman, local mode and tumbling-dependent processes. At 85K, which is in a temperature range where the Raman process dominates, relaxation rates along the g(xx) (g approximately 2.006) and g(yy) (g approximately 2.005) axes are about 2.7-1.5 times faster than along the g(zz) axis (g=2.0023). In highly viscous triethanolamine, contributions from tumbling-dependent processes are negligible. At temperatures above 100K relaxation rates in triethanolamine are unchanged between X-band (9.5GHz) and Q-band (34GHz), so the process that dominates in this temperature interval was assigned as a local mode rather than a thermally activated process. Because the largest proton hyperfine couplings are only 2.2G, spin rotation makes a larger contribution than tumbling-dependent modulation of hyperfine anisotropy. Since g anisotropy is small, tumbling-dependent modulation of g anisotropy makes a smaller contribution than spin rotation at X-band. Although there was negligible impact of methyl rotation on T(1), rotation of t-butyl or t-amyl methyl groups enhances spin echo dephasing between 85 and 150K.