Institute of Atomic and Molecular Physics, Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy, Jilin University, Changchun, China.
Phys Chem Chem Phys. 2018 Jun 13;20(23):16202-16208. doi: 10.1039/c8cp01376d.
We present a strategy by which the stability of tubular boron clusters can be significantly enhanced by doping the B20 cluster with a lithium atom. High-level quantum chemical calculations showed that the lowest energy structures of LiB20 and LiB20- are tubular structures with D10d symmetry, in which the lithium atom is located at the center of the tubular structure. Chemical bonding analysis revealed that the high-symmetry tubular boron clusters are characterized as charge transfer complexes (Li+B20- and Li+B202-), resulting in double aromaticity with delocalized π + σ bonding and strong electrostatic interactions between cationic Li+ and tubular boron motifs with twenty Li-B interactions. The unique bonding pattern of the LiB20 and LiB20- species provides a key driving force to stabilize tubular structures over quasi-planar structures, suggesting that electrostatic interactions resulting from alkali metals might unveil a new clue to the structural evolution of boron clusters.
我们提出了一种策略，通过在 B20 团簇中掺杂一个锂离子，可以显著提高管状硼团簇的稳定性。 高水平的量子化学计算表明，LiB20 和 LiB20-的最低能量结构是具有 D10d 对称性的管状结构，其中锂离子位于管状结构的中心。 成键分析表明，高对称管状硼团簇的特征是电荷转移配合物（Li+B20-和 Li+B202-），具有离域的π+σ键合和阳离子 Li+与具有二十个 Li-B 相互作用的管状硼基元之间的强静电相互作用，导致双芳香性。LiB20 和 LiB20-物种的独特成键模式为稳定管状结构提供了关键驱动力，超过准平面结构，这表明来自碱金属的静电相互作用可能为硼团簇的结构演化提供新线索。
