文献类型：期刊文献

英文题名：Effects of solvent on weak halogen bonds: Density functional theory calculations

作者：Lu, Yunxiang[1,2];Li, Haiying[1,2];Zhu, Xiang[1,2];Liu, Honglai[1,2];Zhu, Weiliang[3]

机构：[1]E China Univ Sci & Technol, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]E China Univ Sci & Technol, Dept Chem, Shanghai 200237, Peoples R China;[3]Chinese Acad Sci, Shanghai Inst Mat Med, Drug Discovery & Design Ctr, Shanghai 201203, Peoples R China

年份：2012

卷号：112

期号：5

起止页码：1421

外文期刊名：INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY

收录：;EI(收录号：20122315081355);WOS:【SCI-EXPANDED(收录号:WOS:000299335900018)】；

基金：Contract grant sponsor: Natural Science Foundation of Shanghai.Contract grant number: 11ZR1408700.Contract grant sponsor: Natural Science Foundation of China.Contract grant number: 20736002.Contract grant sponsor: Creative Team Development Project of Ministry of Education of China.Contract grant number: IRT0721.

语种：英文

外文关键词：weak halogen bonds; solvent effects; PCM; PBE

摘要：In recent years, many applications of solution-phase halogen bonding in anion recognition, catalysis, and pseudorotaxane formation have been reported. Moreover, a number of thermodynamic data of halogen bonding interactions in organic solution are now available. To obtain detailed information of the influence of the surrounding medium on weak halogen bonds, a series of dimeric complexes of halobenzene (PhX) with three electron donors (H2O, HCHO, and NH3) were investigated by means of DFT/PBE calculations in this work. The PCM implicit solvation approach was utilized to include the effects of three solvents (cyclohexane, chloroform, and water) as representatives for a wide range of dielectric constant. In some cases, halogen-bond distances are shown to shorten in solution, accompanied by concomitant elongation of the C?X bonds. For the remaining systems, the intermolecular distances tend to increase or remain almost unchanged under solvent effects. In general, the solvent has a slight destabilizing effect on weak halogen bonds; the strength order of halogen bonds observed in vacuum remains unchanged in liquid phases. Particularly, the interaction strength attenuates in the order I > Br > Cl in solution, consistent with the experimental measurements of weak halogen bond door abilities. The similarities between halogen and hydrogen bonding in solution were also elucidated. The results presented herein would be very useful in future applications of halogen bonding in molecular recognition and medicinal chemistry. (C) 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012