Organosulfur-Based Fullerene Materials

Abstract

Chemical functionalizations of an endohedral metallofullerene, La₂@I_h-C₈₀, and an empty fullerene, C₆₀, are demonstrated using organosulfur compounds. A novel donor–acceptor system of La₂@I_h–C₈₀-exTTF (3) synthesized using the Prato reaction shows photo-induced intramolecular charge separation. On the other hand, the photoreaction of C₆₀ with N-p-toluenesulfonyl sulfilimine affords N-tosyl-1,2-aziridinofullerene (5). The first reversible interconversion of 1,2-aziridinofullerene and 1,6-azafulleroid was found for mono-substituted fullerenes by thermal rearrangement of 5 to 6. S,S-Diphenylsulfilimines (7) with an electron-donating group on the N atom reacts with C₆₀ to afford corresponding aziridinofullerenes (8–10) regioselectively.

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Keywords:

• Aziridinofullerenes
• donor–acceptor systems
• endohedral metallofullerenes
• π-extended tetrathiafulvalene
• sulfilimine

Acknowledgments

Financial support from a Grant-in-Aid for Scientific Research on Innovation Areas (No. 20108001, “pi-Space”); a Grant-in-Aid for Scientific Research (A) (No. 20245006), The Next Generation Super Computing Project (Nanoscience Project); Nanotechnology Support Project; and Grant-in-Aid for Scientific Research on Priority Area (Nos. 20036008, 20038007, 20045002) from the Ministry of Education, Culture, Sports, Science, and Technology of Japan is acknowledged.