Journal of the American Chemical Society, Vol.116, No.8, 3460-3464, 1994
Nonvertical Triplet Excitation Transfer to Arylalkene Accepters - Further Evidence That Double-Bond Torsion Is Unimportant
Time-resolved kinetic absorption spectrophotometry and photoacoustic calorimetry have been employed in a study of the kinetics and energetics of triplet excitation transfer to a series of arylalkene accepters. Both the cis and trans isomers of beta-methylstyrene are able to achieve significant relaxation in the triplet state. Nonvertical behavior is observed only for the cis isomer, for which single-bond torsions are expected to contribute to the measured relaxation. A comparison of the behavior of tetraphenylallene and its model, 1,1-diphenylethylene, is also revealing. Relaxation through double bond torsion in the allene triplet state leads to an "allyl-vinyl" biradical of particularly low energy. Measured energy transfer rate constants for the two molecules display a close correspondence. These results provide further compelling evidence for a recently proposed model for the nonvertical excitation transfer process dominated by single bond torsional modes.
Keywords:ENERGY-TRANSFER;PHOTOACOUSTIC CALORIMETRY;PULSE-RADIOLYSIS;CIS-STILBENE;STATE;DERIVATIVES;RELAXATION;ENERGETICS;LIFETIMES;DESIGN