Abstract
We report easy preparation of recently discovered highly chlorinated fullerenes T h–C 60Cl 24, C 1–C 60Cl 28, and D 3 d –C 60Cl 30 in high-temperature reactions of C 60 with PCl 5 and ICl. Formation and interconversion of chlorofullerenes was investigated in details for C 60–ICl system. C 60Cl 28 is the least stable chlorofullerene that undergoes rearrangement (accompanied by partial chlorine elimination) into more stable T h-C 60Cl 24 under more drastic reaction conditions (increased temperature and time of chlorination). T h-C 60Cl 24 yields D 3 d –C 60Cl 30 at temperatures above 220 °C via a sequence of rearrangements and further addition of chlorine. In contrast to the fullerene reaction with ICl, interaction of C 60 with PCl 5 is very selective with respect to formation of C 60Cl 24 in a wide temperature range. Solid-state electronic (UV–Vis) and vibrational (IR) spectra of chlorinated fullerenes C 60Cl 24, C 60Cl 28, C 60Cl 30 and fluorinated fullerenes C 60F 18 and C 60F 36 were recorded in the spectral range between 30 and 45,000 cm −1. Raman spectra were also acquired for all investigated compounds. Moreover, molecular geometry of the C 60Cl 24 and its theoretical IR-absorption spectrum were calculated using B3LYP/STO-3G chemistry model.
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