UC Unit in Fullerenes: Robust Multicenter Bonds with a Cluster Shape Controlled by Cage Size and Charge Transfer.

Stimulated by the recent successful synthesis and crystallographic characterization of the first diuranium carbide endohedral metallofullerene (EMF) UC@(7)-C ( Zhang et al. ; 2018 ), density functional theory calculations were performed for a series of UC@C (2 = 60, 68, 72, 78, 80, 88, 96, and 104) analogues. The internal UCU bond angle increases from 96.9° in -C to 180.0° in -C, exhibiting cage-size-dependent cluster configuration. However, further evidence suggests that the UC shape may be also affected by the amount of charge transferred from the cluster to the outer cage with 6e and 4e favoring bent and linear, respectively. The change of the bond angle closely correlates with the charge and hybrid state of the internal atom. Significantly, besides the covalent two-center two-electron (2c-2e) U-C bonds, the UC unit always features two 3c-2e bonds regardless of its size, shape, and charge state. Furthermore, for the cluster-cage interactions, besides the dominated electrostatic attractions, all these EMFs show an obvious covalent character with the substantial participation of U 5f valence orbitals.