Persistent C60 anion-radical formation via photoinduced electron transfer from tetraphenylborate and triphenylbutylborate
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Abstract
Photochemical reactions between photo-excited C60 and borates (–BPh4 and –BPh3Bu) have been investigated by steady-state photolysis and laser flash photolysis. On steady-state photolysis of C60 in the presence of the borates in polar solvents, the absorption of C60–˙ increases with irradiation time, suggesting that irreversible photoinduced electron-transfer occurs. By the measurements of the transient absorption spectra, it is indicated that electron transfer takes place from the borate anions to 3C60*, yielding C60–˙ and ˙BPh3R (R = Ph or Bu), in which the latter dissociates into Ph3B and R˙, yielding biphenyl (or octane). Electron-donor ability of –BPh3 Bu is higher than that of –BPh4, while the steady-state photolysis to a C60/borate system shows an opposite tendency. The addition reaction of C60–˙ with Bu˙ yielding BuC60– is more efficient than that with Ph˙ producing PhC60–. The rate constant of electron-transfer via the triplet state of C60 increases with solvent polarity.
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