Synthesis, Spectroscopic and Electrochemical Characterization, and DFT Study of Seventeen C70(CF3)n Derivatives (n=2, 4, 6, 8, 10, 12)

Eight new C70(CF3)n derivatives (n=2, 6, 10, 12) have been synthesized and characterized by UV/Vis and 19F NMR spectroscopy, cyclic voltammetry, and quantum chemical calculations at the DFT level of theory. Nine previously known derivatives of C70(CF3)n with n=2–12 were also studied by cyclic voltammetry (and seven of them by UV/Vis spectroscopy for the first time). Most of the 17 compounds exhibited two or three reversible reductions at scan rates from 20 mV s−1 up to 5.0 V s−1. In general, reduction potentials for the 0/− couple are shifted anodically relative to the C700/− couple. However, the 0/− E1/2 values for a given composition are strongly dependent on the addition pattern of the CF3 groups. The data show that the addition pattern is as important, if not more important in some cases, than the number of substituents, n, in determining E1/2 values. An analysis of the DFT‐predicted LUMOs indicates that addition patterns that have non‐terminal double bonds in pentagons result in derivatives that are strong electron acceptors. C70 fullerene clectrochemistry: An electrochemical and DFT study of 17 C70(CF3)n derivatives (see graphic) has shown that E1/2 values for isomers of a given composition can vary by nearly 0.5 V.