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Four isomers are currently known for the trioxygenated fullerene derivative C(60)(O)(3), three regioisomers with all of the oxygen addends as epoxy groups and the unstable ozonide isomer with a 1,2,3-trioxlane ring. Here we report the synthesis of an open-cage isomer for C(60)(O)(3) with a ketolactone moiety embedded into the fullerene skeleton through a three-step procedure mediated by fullerene peroxide chemistry. Two fullerene skeleton carbon-carbon bonds are cleaved in the process. The open-cage derivative C(60)(O)(3) can be converted back to C(60) through deoxygenation with PPh(3). Single crystal X-ray structure confirmed the open-cage structure.

A series of isomerically pure alkynyl-substituted fullerenol derivatives such as C(60)(OH)(6)(O(CH(2))(3)CCH)(2) were synthesized through Lewis acid catalyzed epoxy ring opening and/or S(N)1 replacement reactions starting from the fullerene-mixed peroxide C(60)(O)(t-BuOO)(4). Copper-catalyzed azide-alkyne cycloaddition readily converted the terminal alkynyl groups into triazole groups. Intramolecular oxidative alkyne coupling afforded a fullerenyl crown ether derivative.

Open‐cage fullerenes with a 19‐membered orifice were prepared in three steps from C60. The key step for cage‐opening is aniline mediated ring expansion of a fullerene‐mixed peroxide with a ketolactone moiety on the orifice. Release of ring strain on the spherical fullerene cage served as the main driving force for the efficient cage‐opening sequence. Encapsulation of oxygen could be achieved at room temperature under moderate pressure (50 atm) and the encapsulated oxygen could be released slowly under ambient conditions. The activation energy of the oxygen‐releasing process is 18.8 kcal mol−1 and the half‐life at 37 °C was 73 min, which makes this open‐cage fullerene derivative a potential oxygen‐delivery material. [ABSTRACT FROM AUTHOR]

Abstract: An open‐cage C60 derivative 9 with anilino, hemiketal, and lactone moieties on the edge of the opening was prepared through a fullerene‐mixed peroxide procedure. Key steps include decarbonylation, intramolecular Friedel–Crafts reaction and oxetane ring opening rearrangement. The open‐cage compound 9 readily reacts with various metal salts. A nickel complex was obtained by treating 9 with NiCl2 at r.t. followed by purification on a silica gel column. Single‐crystal X‐ray diffraction analysis showed that the nickel ion is coordinated to two ligands with an octahedral geometry. [ABSTRACT FROM AUTHOR]

Open the cage if you dare: The azahomoazafullerene 1 was prepared from a tert‐butylperoxy‐substituted azafullerene derivative C59NBr(OOtBu)4. Singlet oxygen added to 1 to form an open‐cage azafullerene 2 with a ketoimide moiety on the rim of the orifice. The MALDI‐TOF mass spectrum of the product of the hydrolysis of 1 showed a clear signal for the diazafullerene C58N2 (see structure 3). [ABSTRACT FROM AUTHOR]

Open the cage if you dare: The azahomoazafullerene 1 was prepared from a tert‐butylperoxy‐substituted azafullerene derivative C59NBr(OOtBu)4. Singlet oxygen added to 1 to form an open‐cage azafullerene 2 with a ketoimide moiety on the rim of the orifice. The MALDI‐TOF mass spectrum of the product of the hydrolysis of 1 showed a clear signal for the diazafullerene C58N2 (see structure 3). [ABSTRACT FROM AUTHOR]

An abstract of the article "Synthesis of an Azahomoazafullerene C59N(NH)R and Gas-Phase Formation of the Diazafullerene C58N2" by Huan Huang, Gaihong Zhang, Dian Wang, Nana Xin, Sisi Liang and Nengdong Wang is presented.