Synthesis, Characterization, and Theoretical Study of Stable Isomers of C70(CF3)n (n = 2, 4, 6, 8, 10)

Reaction of C70 with ten equivalents of silver(I) trifluoroacetate at 320–340 °C followed by fractional sublimation at 420–540 °C and HPLC processing led to the isolation of a single abundant isomer of C70(CF3)n for n = 2, 4, 6, and 10, and two abundant isomers of C70(CF3)8. These six compounds were characterized by using matrix‐assisted laser desorption ionization (MALDI) mass spectrometry, 2D‐COSY and/or 1D 19F NMR spectroscopy, and quantum‐chemical calculations at the density functional theory (DFT) level. Some were also characterized by Raman spectroscopy. The addition patterns for the isolated compounds were unambiguously found to be C1‐7,24‐C70(CF3)2, C1‐7,24,44,47‐C70(CF3)4, C2‐1,4,11,19,31,41‐C70(CF3)6, Cs‐1,4,11,19,31,41,51,64‐C70(CF3)8, C2‐1,4,11,19,31,41,51,60‐C70(CF3)8, and C1‐1,4,10,19,25,41,49,60,66,69‐C70(CF3)10 (IUPAC numbering). Except for the last compound, which is identical to the recently reported, crystallographically characterized C70(CF3)10 derivative prepared by a different synthetic route, these compounds have not previously been shown to have the indicated addition patterns. The largest relative yield under an optimized set of reaction conditions was for the Cs isomer of C70(CF3)8 (ca. 30 mol % of the sublimed mixture of products based on HPLC integration). The results demonstrate that thermally stable C70(CF3)n isomers tend to have their CF3 groups arranged on isolated para‐C6(CF3)2 hexagons and/or on a ribbon of edge‐sharing meta‐ and/or para‐C6(CF3)2 hexagons. For Cs‐ and C2‐C70(CF3)8 and for C2‐C70(CF3)6, the ribbons straddle the C70 equatorial belt; for C1‐C70(CF3)4, the para–meta–para ribbon includes three polar hexagons; for C1‐7,24‐C70(CF3)2, the para‐C6(CF3)2 hexagon includes one of the carbon atoms on a C70 polar pentagon. The 10.3–16.2 Hz 7JF,F NMR coupling constants for the end‐of‐ribbon CF3 groups, which are always para to their nearest‐neighbor CF3 group, are consistent with through‐space Fermi‐contact interactions between the fluorine atoms of proximate, rapidly rotating CF3 groups. Isolated isomers: High‐temperature reaction of C70 with Ag(CF3CO2) led to the isolation of a single abundant isomer of C70(CF3)n for n = 2, 4, 6, and 10, and two abundant isomers of C70(CF3)8 (see the Schlegel diagrams). A combination of 19F NMR and Raman spectroscopy and quantum‐chemical calculations were used to demonstrate that the isolated compounds are among the most stable isomers for each C70(CF3)n composition investigated.