Chen Qiang, Gao Ting, Tian Wen-Juan, Bai Hui, Zhang Su-Yan, Li Hai-Ru, Miao Chang-Qing, Mu Yue-Wen, Lu Hai-Gang, Zhai Hua-Jin, Li Si-Dian
Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China.
Phys Chem Chem Phys. 2015 Aug 14;17(30):19690-4. doi: 10.1039/c5cp03178h.
Using the newly discovered borospherenes C3 B39(-) and C2 B39(-) as molecular devices and based on extensive global-minimum searches and first-principles calculations, we present herein the possibility of the first axially chiral metalloborospherenes C3 Ca@B39(+) (, (1)A) and C2 Ca@B39(+) (, (1)A), which are the global minimum and the second lowest-lying isomer of CaB39(+), respectively. These metalloborospherene species turn out to be charge-transfer complexes Ca(2+)@B39(-) in nature, with the Ca centre on the C3 or C2 molecular axis donating one electron to the B39 cage which behaves like a superhalogen. Molecular orbital analyses indicate that C3/C2 Ca(2+)@B39(-) possess the universal bonding pattern of σ plus π double delocalization, similar to their C3/C2 B39(-) parents. Molecular dynamics simulations show that both C3 Ca@B39(+) () and C2 Ca@B39(+) () are dynamically stable at 200 K, with the former starting to fluctuate structurally at 300 K and the latter at 400 K, again similar to C3/C2 B39(-). The infrared and Raman spectra of C3/C2 Ca@B39(+) (/) are simulated and compared with those of C3/C2 B39(-) to facilitate their forthcoming experimental characterization.
利用新发现的硼球烯C3B39(-)和C2B39(-)作为分子器件，并基于广泛的全局最小值搜索和第一性原理计算，我们在此展示了首例轴向手性金属硼球烯C3Ca@B39(+) (, (1)A)和C2Ca@B39(+) (, (1)A)的可能性，它们分别是CaB39(+)的全局最小值异构体和第二低能异构体。这些金属硼球烯物种实际上是电荷转移复合物Ca(2+)@B39(-)，Ca中心位于C3或C2分子轴上，向表现得像超卤素的B39笼捐赠一个电子。分子轨道分析表明，C3/C2 Ca(2+)@B39(-)具有σ加π双离域的通用键合模式，类似于它们的C3/C2 B39(-)母体。分子动力学模拟表明，C3 Ca@B39(+) ()和C2 Ca@B39(+) ()在200 K时都是动态稳定的，前者在300 K时开始结构波动，后者在400 K时开始波动，同样类似于C3/C2 B39(-)。模拟了C3/C2 Ca@B39(+) (/)的红外和拉曼光谱，并与C3/C2 B39(-)的光谱进行了比较，以促进它们即将进行的实验表征。
