U₂O@C₇₆: Non-Isolated-Pentagon-Rule Cages Prevail with the U₂O Configuration Determined by Cage Shape and Dominated...

Endohedral clusterfullerenes (ECFs) are fullerene cages with various metallic clusters trapped inside. So far, the actinide-based ECFs are rather scarce with their possible structures and chemistry remaining largely unexplored. Herein, density functional theory calculations characterized that the recently synthesized U₂O@C₇₆ could be U₂O@C(17 490)-C₇₆ or U₂O@C₂(19 138)-C₇₆, whose cages have two or one pentagon adjacencies (PAs) and thus both violate the isolated pentagon rule (IPR). It is noteworthy that they are the first actinide-based ECFs bearing non-IPR outer cages. They are also the first C(17 490)- and C₂(19 138)-C₇₆-based oxide ECFs. Moreover, U₂O@C₂(19 138)-C₇₆ is the first example of a hexavalent metal cluster within the C₂(19 138)-C₇₆ cage. Interestingly, although trapped by the two same-sized cages, the U₂O unit exhibits a bent and a perfect linear configuration, respectively, indicative of the crucial role of cage shape in steering the internal cluster configuration. Their electronic structures can be formally described as (U₂O)⁶⁺@C₇₆^6- with primary electrostatic attractions and secondary covalent interactions between cluster and cage. Significantly, bonding analyses reveal that the encaged U₂O moiety may only features two three-center, two-electron (3c-2e) U-O-U bonds with completely absent common two-center bonds.