Structure of [60]fullerene with a mobile lithium cation inside
Structure of [60]fullerene with a mobile lithium cation inside
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DOI：
10.1098/rsos.180337
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发表时间：
2018-07-01
影响因子：
3.5
通讯作者：
Kokubo, Ken
中科院分区：
文献类型：
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作者：
Aoyagi, Shinobu;Miwa, Kazuhira;Kokubo, Ken
用同步辐射X-射线衍射法测定了含锂离子的[60]富勒烯晶体(Li+@C-60)的结构，以了解包裹的Li+阳离子的静电和热性质。虽然[Li+@C-60](TFPB-)中心点C4H10O和[Li+@C-60[(TFSL(-))]中心点CH2Cl2中的Li+离子表现出严重的取向无序，但由于与C-60笼外配位阴离子的静电作用，Li+离子在特定的位置上是有序的。与[Li+@C-60](PF6-)和原始C-60不同，[Li-@C-60](ClO4-)中的Li+@C-60分子具有岩盐型立方结构，即使在100K也是完全无序的，球壳电荷密度几乎均匀(通过ClO4-四面体的八面体配位)，并且没有取向有序。[Li+@C-60(-)](NiOEP)中心点CH-Cl-2(2)中的单键(Li+@C-60)(2)在400K下仍具有热稳定性，形成的Li+-C键比[Li+@C-60](PF6-)中的Li+-C键短，抑制了Li+阳离子的旋转运动。
The structure of crystalline [60]fullerene with a lithium cation inside (Li+@C-60) was determined by synchrotron radiation X-ray diffraction measurements to understand the electrostatic and thermal properties of the encapsulated Li+ cation. Although the C-60 cages show severe orientation disorder in [Li+@C-60](TFPB-)center dot C4H10O and [Li+@C-60[(TFSl(-))center dot CH2Cl2, the Li+ cations are rather ordered at specific positions by electrostatic interactions with coordinated anions outside the C-60 cage. The Li+@C-60 molecules in [Li-@C-60](ClO4-) with a rock-salt-type cubic structure are fully disordered with almost uniform spherical shell charge densities even at 100 K by octahedral coordination of ClO4- tetrahedra) and show no orientation ordering, unlike [Li+@C-60](PF6-) and pristine C-60. Single-bonded (Li+@C-60)(2) dithers in [Li+@C-60(-)](NiOEP)center dot CH-Cl-2(2) are thermally stable even at 400 K and form Li+-C bonds which are shorter than Li+-C bonds in [Li+@C-60](PF6-) and suppress the rotational motion of the Li+ cations.