Abstract
Laser flash photolysis (LFP), low-field chemically induced dynamic nuclear polarization (CIDNP), and time-resolved electron paramagnetic resonance (TREPR) techniques have been used for the comparative study of magnetic field and spin effects in acyl−ketyl and bis(ketyl)biradicals formed during the photolysis of 2-hydroxy-2,12-dimethylcyclododecanone (1-OH) and 2,12-dihydroxy-2,12-dimethylcyclododecanone (2-OH), respectively. The short biradical lifetime, the small magnetic field effect (MFE) on a biradical lifetime, and the low intensity of spin-correlated radical pair (SCRP) polarization observed during the photolysis of 1-OH indicate that the main channel of intersystem crossing in acyl−ketyl biradical is spin−orbit coupling (SOC). For bis(ketyl) biradicals observed during the photolysis of 2-OH, SOC is of minor importance, and both MFE and SCRP polarization are much larger. It is shown that the presence of significant SOC in biradicals can result in an increase of the CIDNP intensity at low magnetic fi...
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