Chen Weihong, Li Jing, Liu Jiayuan, Sun Weiming, Li Zhiru, Li Ying
Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun, 130023, People's Republic of China.
Institute of Applied Chemistry, Hebei North University, Zhangjiakou, 075000, People's Republic of China.
Dalton Trans. 2020 Nov 10;49(43):15267-15275. doi: 10.1039/d0dt03266b.
For the challenge of stabilizing a fullerene-like borospherene, a perfect fullerene-like borospherene B20 with Ih symmetry is stabilized theoretically for the first time by selected 12 η5 (pentahapto)-Mg atoms capped on the 12 B5 pentagons, forming an exohedral metalloborospherene Ih Mg12&B20 molecule. Owing to the pull-push electron transfer relay, the molecule is converted to a spherical electride molecule (Mg2+)12&B2018- + 6e- with multiexcess electrons and high-valent B2018- polyanion with a full-shell electronic configuration, performing the stabilization of the fullerene-like B20 cage. Furthermore, we embed the metal M atom in the B20 cage, forming new endohedral electride molecules (Mg2+)12&(Mn+@B2018-) + (6 + n)e- (M = Li, n = 1 and Mg, n = 2). The embedded atom M increases the excess electron number. Notably, these electride molecules possess two different types of superatomic characteristics, exhibiting the behavior of an electron reservoir. Moreover, a compound (Mg12&B20)2O is designed and obtained, so Mg12&B20 might serve as a nano-building block. In addition, the Mg12&B20 and Mg12&(Mg@B20) electride molecules are efficient external electric field-manipulated nonlinear optical (NLO) switches with high sensitivity and reversibility. The embedding metal atom in the B20 cage can also serve as a new strategy to manipulate NLO switching.
为应对稳定类富勒烯硼球烯的挑战，理论上首次通过在12个B5五边形上帽盖选定的12个η5（五配位）-Mg原子，稳定了具有Ih对称性的完美类富勒烯硼球烯B20，形成了外表面金属硼球烯Ih Mg12&B20分子。由于推拉电子转移中继，该分子转变为具有多个多余电子的球形电子化物分子(Mg2+)12&B2018- + 6e-以及具有满壳层电子构型的高价B2018-聚阴离子，实现了类富勒烯B20笼的稳定。此外，我们将金属M原子嵌入B20笼中，形成新的内包电子化物分子(Mg2+)12&(Mn+@B2018-) + (6 + n)e-（M = Li，n = 1；Mg，n = 2）。嵌入的原子M增加了多余电子数。值得注意的是，这些电子化物分子具有两种不同类型的超原子特征，表现出电子储存库的行为。此外，设计并获得了一种化合物(Mg12&B20)2O，因此Mg12&B20可能用作纳米构建单元。此外，Mg12&B20和Mg12&(Mg@B20)电子化物分子是具有高灵敏度和可逆性的高效外部电场操纵非线性光学（NLO）开关。在B20笼中嵌入金属原子也可作为操纵NLO开关的一种新策略。
