Magnetic field effects on hydrogen abstraction of thiobenzophenone as a probe of microviscosity

Article abstract of DOI:10.1021/jp108898a

Hydrogen abstraction reactions of thiobenzophenone with thiophenol in solutions of varying viscosities (?· = 0.29-42.0 cP) were studied by a nanosecond laser flash photolysis under magnetic fields of 0-15.5 T. In alcoholic solutions, the escaped radical yield (Y) of thiobenzophenone ketyl radical showed appreciable magnetic field effects (MFEs). The observed MFEs can be interpreted with the ??g mechanism through the triplet radical pair. The relative escaped radical yield (R(1.7T) = Y(1.7T)/Y(0T)) decreased with increasing ?· at 0 < ?· a?? 3.33 cP, but then the yield increased with increasing ?· at 3.33 cP < ?· a?? 22.2 cP. At much higher viscosity 22.2 cP < ?· a?? 42 cP, R(1.7T) values become 1.0 within experimental errors. Such quenching of MFE was explained by the spin-orbit coupling recombination of close radical pairs associated with high viscosity. The MFEs on the present reaction is extremely sensitive to the solvent viscosity in the vicinity of the radical pairs. Using this probe reaction, microviscosities of sodium dodecyl sulfate (SDS) and Brij35 micellar solutions were estimated. ? 2011 American Chemical Society.