Building Carbon Bridges on and between Fullerenes in Helium Nanodroplets

We report the observation of sequential encounters of fullerenes with C atoms in an extremely cold environment. Experiments were performed with helium droplets at 0.37 K doped with C60 molecules and C atoms derived from a novel, pure source of C atoms. Very high-resolution mass spectra revealed the formation of carbenes of the type C60(C:)n with n up to 6. Bridge-type bonding of the C adatoms to form the known dumbbell C60═C═C60 also was observed. Density functional theory calculations were performed that elucidated the carbene character of the C60(C:)n species and their structures. Mass spectra taken in the presence of water impurities and in separate experiments with added H2 also revealed the formation of the adducts C60C(n)(H2O)n and C60C(n)(H2)n probably by H-OH and H-H bond insertion, respectively, and nonreactivity for the dumbell. So C adatoms that form carbenes C60(C:)n can endow pristine C60 with a higher chemical reactivity.