First Synthesis and Characterization of CH(4)@C(60)

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.