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Electrochemical behavior of C(60)(CF(2))(n), n = 1, 2 and C(60)(CCl(2)) has been investigated. [6,6]-Opened C(60)(CF(2)) and cis-2-C(60)(CF(2))(2) exhibit reversible reductions at potentials 150 and 145 mV more positive than C(60), unlike the related [6,6]-closed C(60)(CCl(2)), which shows reduction at the potential close to that for C(60). The structures, electron localization and lifetimes of the observed radical anions C(60)(CF(2))(-*) and cis-2-C(60)(CF(2))(2)(-*) have been elucidated by the ESR study and DFT calculations. The protonation pathway of decay of C(60)(CF(2))(-*) yields [6,6]-opened 1,9-dihydro-(1a,1a-difluoro-1aH-1(9)a-homo(C(60)-I(h))fullerene, C(60)(CF(2))H(2), which becomes the first characterized derivative of [6,6]-opened C(60)(CF(2)). DFT calculations of the structure and electron affinity of a number of homofullerene structures have been carried out to rationalize the experimental findings.

Two series of germanium compounds, (pTol) 3 Ge-MMe 3 (M = Si (1), Ge (2), Sn (3)) and (Me 3 Si) 3 Ge-MPh 3 (M = Ge (4), Sn (5)), were prepared using lithium or potassium intermediates. The changing of the reaction conditions results in trigermane Ph 3 Ge-Ge(SiMe 3 ) 2 -GePh 3 (6). The molecular structures of 1, 2, and 6 were investigated by X-ray analysis. By UV/visible spectroscopy it is established that introduction of a tin atom results in a significant bathochromic absorption shift. Furthermore, according to cyclic voltammetry, oxidation potentials decrease in the order 1 > 2 > 3. The electronic structures of 1−4 and related (Me 3 Si) 3 GeSiPh 3 were investigated by DFT calculations. Fluorescence properties of 1−3 were studied in the solid state and in solution; for compound 3 phosphorescence (lifetime is 4.58 ms) is observed in the solid state.