Lawrence Berkeley National Laboratory
Ultrastable actinide endohedral borospherenes.
- Author(s): Wang, Cong-Zhi
- Bo, Tao
- Lan, Jian-Hui
- Wu, Qun-Yan
- Chai, Zhi-Fang
- Gibson, John K
- Shi, Wei-Qun
- et al.
Published Web Locationhttps://doi.org/10.1039/c7cc09837e
Since the discovery of the first all-boron fullerenes B40-/0, metal-doped borospherenes have received extensive attention. So far, in spite of theoretical efforts on metalloborospherenes, the feasibility of actinide analogues remains minimally explored. Here we report a series of actinide borospherenes AnBn (An = U, Th; n = 36, 38, and 40) using DFT-PBE0 calculations. All the AnBn complexes are found to possess endohedral structures (An@Bn) as the global minima. In particular, U@B36 (C2h, 3Ag) and Th@B38 (D2h, 1Ag) exhibit nearly ideal endohedral borospherene structures. The C2h U@B36 and D2h Th@B38 complexes are predicted to be highly robust both thermodynamically and dynamically. In addition to the actinide size match to the cage, the covalent character of the metal-cage bonding in U@B36 and Th@B38 affords further stabilization. Bonding analysis indicates that U@B36 and Th@B38 can be qualified as 32-electron systems, and Th@B38 exhibits 3D aromaticity with σ plus π double delocalization bonding. The results demonstrate that doping with appropriate actinide atoms is promising to stabilize diverse borospherenes, and may provide routes for borospherene modification and functionalization.