The endohedral fullerene CH 4 @C 60 , in which each C 60 fullerene cage encapsulates a single methane molecule, has been synthesized for the first time. Methane is the first organic molecule, as well as the largest, to have been encapsulated in C 60 to date. The key orifice contraction step, a photochemical desulfinylation of an open fullerene, was completed, even though it is inhibited by the endohedral molecule. The crystal structure of the nickel(II) octaethylporphyrin/ benzene solvate shows no significant distortion of the carbon cage, relative to the C 60 analogue, and shows the methane hydrogens as a shell of electron density around the central carbon, indicative of the quantum nature of the methane. The 1 H spin‐lattice relaxation times ( T 1 ) for endohedral methane are similar to those observed in the gas phase, indicating that methane is freely rotating inside the C 60 cage. The synthesis of CH 4 @C 60 opens a route to endofullerenes incorporating large guest molecules and atoms.

We report the combinatorial preparation and high-throughput screening of a library of modified electrodes designed to catalyze the oxidation of NADH. Sixty glassy carbon electrodes were covalently modified with ruthenium(II) or zinc(II) complexes bearing the redox active 1,10-phenanthroline-5,6-dione (phendione) ligand by electrochemical functionalization using one of four different linkers, followed by attachment of one of five different phendione metal complexes using combinatorial solid-phase synthesis methodology. This gave a library with three replicates of each of 20 different electrode modifications. This library was electrochemically screened in high-throughput (HTP) mode using cyclic voltammetry. The members of the library were evaluated with regard to the surface coverage, midpeak potential, and voltammetric peak separation for the phendione ligand, and their catalytic activity toward NADH oxidation. The surface coverage was found to depend on the length and flexibility of the linker and the geometry of the metal complex. The choices of linker and metal complex were also found to have significant impact on the kinetics of the reaction between the 1,10-phenanthroline-5,6-dione ligand and NADH. The rate constants for the reaction were obtained by analyzing the catalytic currents as a function of NADH concentration and scan rate, and the influence of the surface molecular architecture on the kinetics was evaluated.

An open-cage fullerene incorporating phosphorous ylid and carbonyl group moieties on the rim of the orifice can be filled with gases (H 2 ,He, Ne) in the solid state,and the cage opening then contracted in situ by raising the temperature to complete an intramolecular Wittig reaction, trapping the atom or molecule inside.K nown transformations complete conversion of the product fullerene to C 60 containing the endohedral species.A sw ell as providing an improved synthesis of large quantities of 4 He@C 60 ,H 2 @C 60 ,and D 2 @C 60 ,the method allows the efficient incorporation of expensive gases such as HD and 3 He,t op repare HD@C 60 and 3 He@C 60 .T he method also enables the first synthesis of Ne@C 60 by molecular surgery,and its characterization by crystallography and 13 CNMR spectroscopy.

Synthesis of Ar@C60 is described, using a route in which high-pressure argon filling of an open-fullerene and photochemical desulfinylation are the key steps for >95% encapsulation of the noble gas....