Photoinduced Electron Transfer fromN,N-Dimethylaniline to Pyrrolidinofullerenes (C60(C3H6N)R):  Emphasized Substituent Effects with Solvent Polarity Change

摘要: Photoinduced electron-transfer reactions of pyrrolidinofullerenes {C60(C3H6N)R; R = H (1), C6H4NO2-p (2), C6H4CHO-p (3), C6H5 (4), C6H4OMe-p (5), and C6H4NMe2-p (6)} with N,N-dimethylaniline have been systematically studied by means nanosecond laser photolysis. From the direct observation rises anion radicals accompanied decays triplet states fullerenes, rate constants (kET) via were evaluated in polar solvents. Although kET values are considerably decreased substituents as compared that pristine C60, electron is accepted C60 moiety. Among derivatives, 2 3 electron-withdrawing groups larger than those 4 1. In less solvent, such a substituent effect becomes prominent decrease values, which accord reactivity−selectivity principle. This behavior can be explained Rehm−Weller relation and/or Marcus equatio...