Th@C76. Computational characterization of larger actinide endohedral fullerenes
Th@C76. Computational characterization of larger actinide endohedral fullerenes
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DOI：
10.1002/qua.25501
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发表时间：
2018-03-05
影响因子：
2.2
通讯作者：
Zhao, Yujun
中科院分区：
文献类型：
--
作者：
Jin, Peng;Liu, Chang;Zhao, Yujun
在最近的实验中成功地制备了锕系元素内嵌富勒烯Th@C-76（Wang等人，J. Am. 2017，139，5110），但没有任何结构信息。在这项工作中，密度泛函理论计算表明，这种新的分子带有一个T-d（19151）-C-76笼遵守孤立的五边形规则。内部的Th原子是偏心的，位于一个sumanene型的六方环下，形式上为碳笼提供4 e。金属的位置是合理的负电荷笼的结构和电荷分布。有趣的是，基于笼对称性和定位的过渡态结构，发现了高温下金属在C-76笼内的八面体状动力学轨迹。此外，Th@C-76的红外，NMR和UV/维斯光谱进行了模拟，以协助未来的实验表征。
The actinide endohedral fullerene Th@C-76 was successfully prepared in a very recent experiment (Wang et al., J. Am. Chem. Soc. 2017, 139, 5110) yet without any structural information. In this work, density functional theory calculations revealed that this novel molecule bears a T-d(19151)-C-76 cage obeying the isolated pentagon rule. The internal Th atom is off-centered and resides under a sumanene-type hexagonal ring, formally donating 4e to the carbon cage. The metal position was rationalized by the structure and charge distribution of the negatively charged cage. Interestingly, an octahedron-like dynamic trajectory of metal inside the C-76 cage at high temperature was found based on the cage symmetry and located transition state structures. Furthermore, the infrared, NMR, and UV/vis spectra of Th@C-76 were simulated to assist future experimental characterization.