[6,6]-open and [6,6]-closed isomers of C70(CF2): synthesis, electrochemical and quantum chemical investigationстатья

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[1] [6,6]-open and [6,6]-closed isomers of c70(cf2): synthesis, electrochemical and quantum chemical investigation / N. A. Samoylova, N. M. Belov, V. A. Brotsman et al. // Chemistry - A European Journal. — 2013. Novel difluoromethylenated [70]fullerene derivatives, C70(CF2)n, n=1–3, were obtained by the reaction of C70 with sodium difluorochloroacetate. Two major products, isomeric C70(CF2) monoadducts with [6,6]-open and [6,6]-closed configurations, were isolated and their homofullerene and methanofullerene structures were reliably determined using a variety of methods including X-ray analysis and high-level spectroscopic techniques. The [6,6]-open C70(CF2) constitutes the first homofullerene example of a non-hetero [70]fullerene derivative in which functionalization involves the most reactive bond in the polar region of the cage. Voltammetric estimation of the EA of the C70(CF2) isomers showed that it is substantially higher for the [6,6]-open isomer (since the 70π-conjugated system is retained) as compared to that of the [6,6]- closed form, the latter being similar to the EA of pristine C70. In situ ESR spectroelectrochemical investigation of the C70(CF2) radical anions along with DFT calculations of the hyperfine coupling constants evidence the first example of an interconversion between the [6,6]-closed and [6,6]-open forms of a cage-modified fullerene driven by an electrochemical one-electron transfer. Thus, [6,6]-closed C70(CF2) constitutes an interesting example of a redox switchable fullerene derivative. [ DOI ]

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