Structural criteria for the design of anion receptors: The interaction of halides with electron-deficient arenes
Structural criteria for the design of anion receptors: The interaction of halides with electron-deficient arenes
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DOI：
10.1021/ja063460m
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发表时间：
2007-01-10
影响因子：
15
通讯作者：
Hay, Benjamin P.
中科院分区：
文献类型：
--
作者：
Berryman, Orion B.;Bryantsev, Vyacheslav S.;Hay, Benjamin P.
本文改进了缺电子芳烃与卤化物阴离子之间相互作用的性质。结论是基于(i)含有1,2,4,5-四氰苯（TCB）和18-冠-6的碱卤化物盐的新晶体结构，（ii）对剑桥结构数据库中发现的晶体结构的评估，以及（iii） MP2/ 8- cc- pvdz计算的F-、Cl-和Br-与TCB、1,3,5-三氰苯、三嗪和六氟苯的配合物。当卤化物位于π系统平面以上时，结果确定了三种明显不同类型的配合物：强共价sigma配合物，弱共价给体- π -受体配合物和非共价阴离子- π配合物。当芳基C-H基团存在时，第四种相互作用导致C-H中心点中心点X-氢键。表征四种可能的结合基序所遇到的不同几何形状，为设计含有缺电子芳烃的宿主体系结构提供了所需的标准。
This paper refines the nature of the interactions between electron-deficient arenes and halide anions. Conclusions are based on (i) new crystal structures containing alkali halide salts with 1,2,4,5-tetracyanobenzene (TCB) and 18-crown-6, (ii) evaluation of crystal structures found in the Cambridge Structural Database, and (iii) MP2/aug-cc-pVDZ calculations of F-, Cl-, and Br- complexes with TCB, 1,3,5-tricyanobenzene, triazine, and hexafluorobenzene. When the halide lies above the plane of the pi system, the results establish that three distinctly different types of complexes are possible: strongly covalent sigma complexes, weakly covalent donor-pi-acceptor complexes, and noncovalent anion-pi complexes. When aryl C-H groups are present, a fourth type of interaction leads to C-H center dot center dot center dot X- hydrogen bonding. Characterization of the different geometries encountered with the four possible binding motifs provides criteria needed to design host architectures containing electron-deficient arenes.