Evaluation of the chemo- and shape-selective association of a bowl-type dodecavanadate cage with an electron-rich group
Evaluation of the chemo- and shape-selective association of a bowl-type dodecavanadate cage with an electron-rich group
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碗型十二钒酸盐笼与富电子基团的化学和形状选择性结合的评估
DOI：
10.1039/c9dt00462a
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发表时间：
2019
影响因子：
4
通讯作者：
Hayashi Yoshihito
中科院分区：
文献类型：
--
作者：
Kikukawa Yuji;Kitajima Hiromasa;Hayashi Yoshihito
通过监测V12空腔中客体的存在或不存在引起VO5单元的翻转，评价了半球形十二钒酸盐(V12)与中性分子客体之间的主客体相互作用。在N，N-二甲基甲酰胺(DMF)中，V12采用无客体形式(V12无)。通过加入乙腈、硝基甲烷和二氯甲烷等客体分子，观察到V12(客体)的结构转变，其亲和常数分别为137±10M−1、0.14±0.1M−1和0.15±0.1M−1。在1，2-二氯乙烷、1，2-二溴乙烷和1，2-二碘乙烷中，其吸附常数分别为35±5M−1、114±5M−1和2.1±0.5M−1。环碳酸酯、5元和6元内酯、环丁酮和己醛被插入到V12宿主中，而非环碳酸酯、非环和7元环酯、带5元环的酮和苯甲醛对客体插入没有影响。V12主客体偏爱富含电子基团的客体，碗状结构表现出与客体独特的择形相互作用。
The host–guest interaction between a half spherical-type dodecavanadate (V12) and a neutral molecule guest was evaluated by monitoring the flip of a VO5 unit caused by the presence or absence of a guest in the cavity of V12. In N,N-dimethylformamide (DMF), V12 adopted the guest-free form (V12-free). By the addition of several guest molecules, such as acetonitrile, nitromethane, and dichloromethane, the structural conversion to the guest-inserted form (V12(guest)) was observed with the affinity constants of 137 ± 10 M−1, 0.14 ± 0.1 M−1, and 0.15 ± 0.1 M−1, respectively. In the case of 1,2-dichloroethane, 1,2-dibromoethane, and 1,2-diiodoethane, the constants were 35 ± 5 M−1, 114 ± 5 M−1, and 2.1 ± 0.5 M−1, respectively, suggesting that the bromo group is the best fit to the cavity of the bowl. A cyclic carbonate, 5- and 6-membered lactones, cyclobutanone, and hexanal were inserted into the V12 host, while a non-cyclic carbonate, non-cyclic and 7-membered cyclic ester, a ketone with a 5-membered ring, and benzaldehyde showed no effect on the guest insertion. The V12 host preferred to hold a guest with an electron-rich group, and the bowl-type structure showed the unique shape-selective interaction with the guest.