Photoinduced Electron Transfer in Solid C60 Donor/Acceptor Complexes Studied by Light-Induced Electron-Spin Resonance

Abstract

ABSTRACT Light-induced ESR (LESR) spectroscopy was used to study photoinduced electron transfer (PIET) in the crystals of the C60 donor/acceptor complexes. High-field LESR signals attributed to (g = 1.9984−1.9992 and ΔH = 3−6 G at 100 K) were observed in fullerene complexes with Leuco Crystal Violet (LCV·C60·C6H5Cl, 1), N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPDA·C60, 2), and bianthrone ((BA)2C60, 3), whereas a low-field LESR signal in 2 was attributed to TMPDA•+. Microwave power studies reveal two independent spins in 2 and show high relaxation rates for photoinduced spins on . The LESR signals consist of a major long-lived “persistent” component and a minor “prompt” one, which disappears immediately after light is off. The maximal intensity of the LESR signals was observed for the excitation of 1–3 below 2 eV. This range of photon energy corresponds to direct intermolecular charge transfer from donor to C60 molecules. PIET is temperature activated with Ea = 23, 43 and 49 meV for 1, 2, and 3, respectively. Photoinduced spin susceptibility attains the maximum at 30 K in 1 and decreases with temperature down to 4 K indicating a possible antiferromagnetic interaction of spins, while in 2 it increases with the temperature decrease down to 4 K.