Dynamics of Photoinduced Electron-Transfer Processes in Fullerene-Based Dyads: Effects of Varying the Donor Strength

摘要

Two classes of fullerene-based donor-bridge-acceptor (D-B-A) systems containing donors of varying oxidation potentials have been synthesized. These systems include fullerenes linked to heteroaromatic donor groups (phenothiazine/phenoxazine) as well as substituted anilines (p-anisidine/p-toluidine). In contrast to the model compound, an efficient intramolecular electron transfer is observed from the fullerene singlet excited state in polar solvents. An increase in the rate constant and quantum yield of charge separation (k_(cs) and Φ_(cs)) has been observed for both classes of dyads, with decrease in the oxidation potentials of the donor groups. This observation indicates that the rates of the forward electron transfer fall in the normal region of the Marcus curve. The long-lived charge separation enabled the characterization of electron transfer products, namely, the radical cation of the donor and radical anion of the pyrrolidinofullerene, by using nanosecond transient absorption spectroscopy. The small reorganization energy (λ) of C_(60) coupled with large negative free energy changes (-ΔG°) for the back electron transfer places the back electron process in the inverted region of Marcus curve, thereby stabilizing the electron transfer products.