Journal of the American Chemical Society, Vol.128, No.37, 12268-12280, 2006
Thermally stable perfluoroalkylfullerenes with the skew-pentagonal-pyramid pattern: C-60(C2F5)(4)O, C-60(CF3)(4)O, and C-60(CF3)(6)
Reaction of C-60 with CF3I at 550 degrees C, which is known to produce a single isomer of C-60(CF3)(2,4,6) and multiple isomers of C-60(CF3)(8,10), has now been found to produce an isomer of C-60(CF3)(6) with the C-s-C60X6 skew- pentagonal-pyramid (SPP) addition pattern and an epoxide with the C-s-C60X4O variation of the SPP addition pattern, C-s-C-60(CF3)(4)O. The structurally similar epoxide C-s-C-60(C2F5)(4)O is one of the products of the reaction of C-60 with C2F5I at 430 degrees C. The three compounds have been characterized by mass spectrometry, DFT quantum chemical calculations, Raman, visible, and F-19 NMR spectroscopy, and, in the case of the two epoxides, single-crystal X-ray diffraction. The compound Cs-C-60(CF3)(6) is the first [60]-fullerene derivative with adjacent R-f groups that are sufficiently sterically hindered to cause the (DFT-predicted) lengthening of the cage (CF3)C-C(CF3) bond to 1.60 angstrom as well as to give rise to a rare, non-fast-exchange-limit F-19 NMR spectrum at 20 degrees C. The compounds C-s-C-60(CF3)(4)O and C-s-C-60(C2F5)(4)O are the first poly (perfluoroalkyl) fullerene derivatives with a non-fluorine-containing exohedral substituent and the first fullerene epoxides known to be stable at elevated temperatures. All three compounds demonstrate that the SPP addition pattern is at least kinetically stable, if not thermodynamically stable, at temperatures exceeding 400 degrees C. The high-temperature synthesis of the two epoxides also indicates that perfluoroalkyl substituents can enhance the thermal stability of fullerene derivatives with other substituents.