Single-bonded fullerene dimers, (C60R)2 (R = (2-methoxyphenyl)dimethylsilylmethyl, (isopropoxy)dimethylsilylmethyl, and 2-methoxy-5-methylphenyl), afforded fullerene derivative cations (RC60+) in the presence of an oxidant (I2, CuCl2, or CuBr2), leading to 5- and 7-membered cyclo[60]fullerene derivatives such as cyclo[60]fullerenes containing a Si–O bond, cyclo[60]fullerenes containing a C60–O bond, and dihydrobenzofurano[60]fullerene. The reaction mechanism involved thermal homolytic cleavage to give fullerene radical, oxidation of the radical to generate fullerene cation, and then demethylative cyclization in which the fullerene cationic centers interact with an aromatic group or the oxygen atoms of methoxy groups to produce the cyclized products. Obtained cyclo[60]fullerene derivatives were used in bulk-heterojunctoin organic solar cells and showed moderate power conversion efficiency and respectable open-circuit voltage.
[1] Y. Matsuo, K. Ogumi, Y. Zhang, H. Okada, T. Nakagawa, H. Ueno, A. Gocho, E. Nakamura, J. Mater. Chem. A, in press.