S. Sasaki et al., SPIN-ORBIT-COUPLING INDUCED ELECTRON-SPIN POLARIZATION - INFLUENCE OFHEAVY-ATOM POSITION, Journal of the American Chemical Society, 119(6), 1997, pp. 1323-1327
Echo-detected FT-EPR spectra have been observed for the quinone anion
radical generated from the photoexcitation of duroquinone (DQ) in the
presence of N,N-dimethylaniline (DMA) and its monohalogen substituents
in 1-propanol. When DMA and 4-Cl DMA were used as the electron donor,
the net-emissive polarization due to a triplet mechanism was observed
. In contrast, the electron donors of 4-BrDMA and 4-IDMA gave unusual
net-absorptive (A) CIDEP spectra of the DQ anion radical at the delay
time of 200 ns between the laser and first microwave pulses. It was fo
und that the enhancement factor of the net-A polarization remarkably d
epends on the heavy atom position in the donor. The net-A polarization
observed is attributable to a spin-orbit coupling mechanism (SOCM). S
imple explicit expressions have been given for the electron spin polar
ization generation due to SOCM.