Trapping an unprecedented Ti3C3 unit inside the icosahedral C80 fullerene: a crystallographic survey

The sub-nanometer cavity of fullerene cages is an ideal platform to accommodate otherwise unstable species for accurate structural characterization with, for example, rather accurate single crystal X-ray diffraction (XRD) crystallography. Herein, we report the successful entrapment of an isolated Ti3C3 moiety inside the icosahedral-C80 cage to form Ti3C3@Ih-C80via an arc-evaporation process in the gas phase. The single crystal XRD crystallographic results unambiguously reveal that the C3-unit adopts an unprecedented cyclopropane-like structure which coordinates with the three titanium atoms in an unexpected fashion where the triangular C3-unit is nearly perpendicular to the Ti3-plane. The intercalation of a cyclopropanated C3-unit into the titanium layer is thus unambiguously confirmed. The theoretical results reveal that the Ti3C3 cluster transfers six electrons to the Ih-C80 cage so that each titanium atom has a positive charge slightly above +2 and the C3-unit is negatively charged with about −1. It is noteworthy that this is the first observation of the cyclopropane-coordination fashion in any reported organometallic complex, providing new insights into coordination chemistry.