Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China.
Phys Chem Chem Phys. 2018 Jun 6;20(22):15344-15349. doi: 10.1039/c8cp01769g.
Shortly after the discovery of all-boron fullerenes D2d B40-/0 (borospherenes), the first axially chiral borospherenes C3/C2 B39- were characterized in experiments in 2015. Based on extensive global minimum searches and first-principles theory calculations, we present herein two new axially chiral members to the borospherene family: the aromatic cage-like C2 B34(1) and C2 B35+(2). Both B34(1) and B35+(2) feature one B21 boron triple chain on the waist and two equivalent heptagons and hexagons on the cage surface, with the latter being obtained by the addition of B+ into the former at the tetracoordinate defect site. Detailed bonding analyses show that they follow the universal bonding pattern of σ + π double delocalization, with 11 delocalized π bonds over a σ skeleton. Extensive molecular dynamics simulations show that these borospherenes are kinetically stable below 1000 K and start to fluctuate at 1200 K and 1100 K, respectively. The IR, Raman, and UV-vis spectra of 1 and 2 are computationally simulated to facilitate their experimental characterization.
在全硼富勒烯 D2d B40-/0（硼球烯）被发现后不久，第一个轴向手性硼球烯 C3/C2 B39-于 2015 年在实验中被表征。基于广泛的全局最小搜索和第一性原理理论计算，我们在此提出了硼球烯家族的两个新的轴向手性成员：芳香笼状 C2 B34(1)和 C2 B35+(2)。B34(1)和 B35+(2)都在腰部具有一个 B21 硼三链，在笼状表面具有两个等效的七元和六元环，后者是通过在四配位缺陷位将 B+添加到前者中得到的。详细的键分析表明，它们遵循σ+π 双重离域的通用键合模式，其中 11 个离域π键在σ骨架上。广泛的分子动力学模拟表明，这些硼球烯在 1000 K 以下是动力学稳定的，分别在 1200 K 和 1100 K 开始波动。1 和 2 的红外、拉曼和紫外-可见光谱通过计算模拟进行了模拟，以促进它们的实验表征。
