Structural Criteria for the Design of Anion Receptors: The Interaction of Halides with Electron-Deficient Arenes

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• 作者：Orion B. Berryman ; Vyacheslav S. Bryantsev ; David P. Stay ; Darren W. Johnson ; Benjamin P. Hay
• 刊名：Journal of the American Chemical Society
• 出版年：2007
• 出版时间：January 10, 2007
• 年：2007
• 卷：129
• 期：1
• 页码：48 - 58
• 全文大小：530K
• 年卷期：v.129,no.1(January 10, 2007)
• ISSN：1520-5126

文摘

This paper refines the nature of the interactions between electron-deficient arenes and halideanions. 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 CambridgeStructural 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 ges/gifchars/pi.gif" BORDER=0 >system, the results establish that three distinctly different types of complexes are possible: strongly covalentges/gifchars/sigma.gif" BORDER=0 > complexes, weakly covalent donor-ges/gifchars/pi.gif" BORDER=0 >-acceptor complexes, and noncovalent anion-ges/gifchars/pi.gif" BORDER=0 > complexes. Whenaryl C-H groups are present, a fourth type of interaction leads to C-H · · · X^- hydrogen bonding.Characterization of the different geometries encountered with the four possible binding motifs providescriteria needed to design host architectures containing electron-deficient arenes.