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Novel Oxidative Nucleophilic Chemistry Enroute to The Synthesis of C60 Fullerols

  • Long Y. Chiang (a1), Lee Y. Wang (a1) and John W. Swirczewski (a2)


We have demonstrated a novel cyclosulfation chemistry for the functionalization of C60 Molecules and a new route to the synthesis of fullerol. The cyclosulfation reaction of C60 was performed in neat fuming sulfuric acid at 55–60 °C under N2. Hydrolysis of these derivatives in the presence of water at 85–90 °C or in aqueous NaOH solution at ambient temperature gave the corresponding polyhydroxylated fullerenes (fullerols) in high yield. Various spectroscopie methods were used to resolve the chemical structure of fullerol. An average of 10 to 12 hydroxyl addends was found in fullerols that can be correlated to the structure of polycyclosulfated fullerene precursors containing 5 to 6 cyclosulfate units. The cyclosulfation chemistry is, presumably, initiated by an one-electron oxidation reaction on C60 Molecules, followed by the attack of nucleophilic anionie sulfate species onto the resulting cationic C60 radical intermediates. Further electron oxidation and intramolecular cyclization of the resulting hydrogen sulfated C60 yielded the desired polycyclosulfated C60 products.



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(12) 2-hydroxyethyl hydrogen sulfate was synthesized from the reaction of sulfur trioxide-DMF complex with an excess of ethylene glycol in CH3CN at 65 °C. Infrared spectrum of 2-hydroxyethyl hydrogen sulfate:υmax (KBr) 3320 (br, -OH), 2947, 1706 (s), 1454, 1227 (s), 1060, 1014, 917, 776, and 585 cm-1.
(13) The sulfur binding energy of diethylsulfate was found to center at 169.3 eV (66.6% and FWHM width = 1.65 eV) and 170.5 eV (33.3% and FWHM width = 1.65 eV) in a ratio of 2:1. Whereas the curve-fitting analysis of the sulfur peak in the XPS spectrum of 3 gave four peaks (two sets) with a binding energy centered at 169.2 eV (52.9% and FWHM width = 1.65 eV) and 170.3 eV (26.5% and FWHM width = 1.65 eV) as the first set and at 170.5 eV (13.7% and FWHM width = 1.65 eV) and 171.5 eV (6.8% and FWHM width =1.65 eV) as the second set.
(14) About 2.7 atomic % of carbons with an oxidation state higher than that of the Mono-oxygenated carbons may be contributed from impurities. XPS (atomic %) of 4: C, 74.2; O, 16.0; F, 9.8
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