A time-resolved EPR study of the electron-spin-polarization pathways of p-benzosemiquinone.

Benzoquinone (BQ), deuterobenzoquinone (d4-BQ), and hydroquinone (BQH2) are investigated in ethylene glycol by means of direct detection fast time-resolved EPR spectroscopy after laser flash photolysis. The development of the magnetization as a function of time and magnetic field is obtained and analyzed in terms of the Bloch equations and hyperfine parameters. The signals are attributed to the semiquinones BQH(*) and d4-BQH(*). The presence of 1,2-dihydroxyethyl radicals during the photolysis of BQ and d(4)-BQ is verified. No alkyl radicals are observed in solutions of BQ with excess BQH2. Detailed analysis of the chemically induced dynamic electron polarization spectra with respect to their development in time shows that polarization patterns of the semiquinones can be traced back to a superposition of triplet mechanism and radical pair mechanism, the latter arising from geminate T-pairs. Hence, two independent pathways for polarization are assumed: reaction of triplet benzoquinone with ethylene glycol leads to the semiquinone and dihydroxyethyl radicals with all signals in emission, whereas the reaction of triplet BQ and BQH2 yields two semiquinones exhibiting both net emissive and multiplet emissive/absorptive intensity distributions. Copyright 2001 Academic Press.