Solvent Polarity Effect on Photoinduced Electron Transfer between C60 and Tetramethylbenzidine Studied by Laser Flash Photolysis

Abstract

The photoinduced electron transfer between C{sub 60} and N,N,N{prime},N{prime}-tetramethylbenzidine (NTMB) in polar and nonpolar solvents and their mixtures has been investigated by nanosecond laser flash photolysis/transient absorption spectroscopy in the visible and near-IR regions. The transient absorption bands of the C{sub 60} triplet state ({sup T}C{sub 60}*) and the NTMB radical cation were observed in both nonpolar and polar solvents. In polar solvents such as benzonitrile, the reaction rate constants were determined from the decay of {sup T}C{sub 60}* at 740 nm, which were consistent with the rate constants evaluated from the growth of the NTMB radical cation, suggesting that direct electron transfer occurs from ground-state NTMB to {sup T}C{sub 60}*. In nonpolar solvents such as benzene, the NTMB radical cation and C{sub 60} radical anion were produced immediately after the nanosecond laser pulse, simultaneous with the formation of {sup T}C{sub 60}*, indicating that a different electron transfer mechanism exists in nonpolar solvents. In the solvent mixtures, two simultaneous reaction routes are present for both forward and back electron transfer reactions. Pronounced solvent effects found for electron transfer reaction kinetics and rates are characteristic of the photoinduced electron transfer reactions between C{sub 60} and some kinds of aromatic amines. 25more » refs., 8 figs., 2 tabs.« less