Breathing and twisting: an investigation of framework deformation and guest packing in single crystals of a microporous vanadium benzenedicarboxylate.
Breathing and twisting: an investigation of framework deformation and guest packing in single crystals of a microporous vanadium benzenedicarboxylate.
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DOI：
10.1021/ic1025087
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发表时间：
2011-01
影响因子：
4.6
通讯作者：
Xiqu Wang;J. Eckert;Lumei Liu;A. Jacobson
中科院分区：
文献类型：
--
作者：
Xiqu Wang;J. Eckert;Lumei Liu;A. Jacobson
用单晶X射线衍射法测定了苯二甲酸钒VO（bdc）·Guest的结构，其中客体分子为苯、1，4-环己二烯、1，3-环己二烯、环己烯和环己烷等六环分子.所有的六环客体分子都表现出VO（bdc）通道内的高度有序性。客体和主体骨架之间的相互作用主要是以货车范德华键为主。六环分子在通道中都以人字形或接近平行的模式排列在两列中。堆积将VO（bdc）的空间群对称性从Pnma改变为非中心对称空间群P2（1）2（1）2（1）。VO（bdc）骨架变形，以紧密适应客体分子双柱的形状和厚度变化。除了研究的呼吸变形，一个扭曲变形机制，涉及一个合作的八面体链的旋转伴随着bdc配体的弯曲是显而易见的详细结构数据。从从头计算得到的VO（BDC）框架的显着的灵活性的更多的定量信息。
The structural details of the compounds vanadium benzenedicarboxylate VO(bdc)·Guest, where the Guests are the absorbed six-ring molecules: benzene, 1,4-cyclohexadiene, 1,3-cyclohexadiene, cyclohexene and cyclohexane, have been determined from single crystal X-ray data. All of the six-ring guest molecules show a high degree of ordering inside the channels of VO(bdc). The interactions between the guests and the host framework are dominated by van der Waals bonding. The six-ring molecules are all packed in two columns in the channels, either in herringbone or close to parallel patterns. The packing changes the space group symmetry of VO(bdc) from Pnma to the noncentrosymmetric space group P2(1)2(1)2(1). The VO(bdc) framework deforms to closely adapt to the shape and thickness changes of the double columns of the guest molecules. In addition to the well studied breathing deformation, a twisting deformation mechanism that involves a cooperative rotation of the octahedral chains accompanied by bending of the bdc ligand is apparent in the detailed structural data. More quantitative information on the remarkable flexibility of the VO(bdc) framework was obtained from ab initio calculations.