Quantum chemical calculations and NMR spectroscopic data suggest that the two isomers of Y@C82(CF3)5 prepared by trifluoromethylation of the endohedral metallofullerene (EMF) contain chains of four 1,4‐C6(CF3)2 edge‐sharing hexagons (see picture). In striking contrast to the empty fullerenes, which form complex mixtures with up to 22 CF3 groups, EMF Y@C82 only forms products with one, three, and five CF3 groups.
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