Zhao Xiao-Ni, Wei Zhi-Hong, Li Si-Dian
Key Laboratory of Chemical Biology and Molecular Engineering of Education Ministry, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China.
Molecules. 2024 Dec 13;29(24):5879. doi: 10.3390/molecules29245879.
Endohedral metallo-borospherenes M@B have received considerable attention since the discovery of B in 2014. However, the coordination bonding nature of most of actinide-doped endohedral An@B still remains in dispute or unexplored. Extensive and systematic first-principles theory calculations performed herein unveil the ground states of triplet U@B (, , A), quartet U@B (, , B), quintet Np@B (, , A), sextet Np@B (, , A), septet Pu@B (, , A), octet Am@B (, , A), and octet Cm@B (, , A) at the coupled-cluster with triple excitations CCSD(T) level. Detailed principal interacting spin orbital (PISO) and adaptive natural density partitioning (AdNDP) analyses reveal their coordination bonding patterns and show that, with the numbers of unpaired -electrons in parallel spins varying from n = 2, 3, 4, 5, 6, 7, to 7 in these complexes, the percentage contribution of the An 5f-involved PISO pairs to overall coordination bonding interactions decreases monotonously from 41% to 1%, and the contribution of An 6d-involved PISO pairs increases monotonously from 47% to 72%, while the marginal contribution of An 7s-involved PISO pairs remains basically unchanged (4~7%). The IR, Raman, and photoelectron spectra of the most concerned species are computationally simulated to facilitate their characterizations in future experiments.
自2014年硼球烯被发现以来，内嵌金属硼球烯M@B受到了广泛关注。然而，大多数锕系元素掺杂的内嵌化合物An@B的配位键本质仍存在争议或未被探索。本文进行了广泛而系统的第一性原理理论计算，揭示了在耦合簇三重激发CCSD(T)水平下，三重态U@B(,, A)、四重态U@B(,, B)、五重态Np@B(,, A)、六重态Np@B(,, A)、七重态Pu@B(,, A)、八重态Am@B(,, A)和八重态Cm@B(,, A)的基态。详细的主要相互作用自旋轨道(PISO)和自适应自然密度划分(AdNDP)分析揭示了它们的配位键模式，并表明，在这些配合物中，平行自旋中未成对 -电子的数量从n = 2、3、4、5、6、7变化到7时，参与配位键相互作用的An 5f相关PISO对的贡献百分比从41%单调下降到1%，参与配位键相互作用的An 6d相关PISO对的贡献从47%单调增加到72%，而参与配位键相互作用的An 7s相关PISO对的边际贡献基本保持不变(4~7%)。对最受关注的物种的红外、拉曼和光电子能谱进行了计算模拟，以促进它们在未来实验中的表征。
