文献类型：期刊文献

英文题名：How Does Halogen Bonding Behave in Solution? A Theoretical Study Using Implicit Solvation Model

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

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：2011

卷号：115

期号：17

起止页码：4467

外文期刊名：JOURNAL OF PHYSICAL CHEMISTRY A

收录：;EI(收录号：20111813955583);WOS:【SCI-EXPANDED(收录号:WOS:000289824500038)】；

基金：This work was financially supported by the Natural Science Foundation of Shanghai (Grant 11ZR1408700), the National Natural Science Foundation of China (Grant 20736002), the Program for Changjiang Scholars and Innovative Research Team in the University of China (Grant IRT0721), and the 111 Project of China (Grant B08021).

语种：英文

外文关键词：Ions - Gases - Binding energy - Quantum chemistry - Acetone - Solvation - Chlorine compounds - Continuum mechanics - Hydrogen bonds - Organic solvents

摘要：A systematic study of halogen bonding interactions in gas phase and in solution was carried out by means of quantum chemical DFT/B3LYP method. Three solvents with different polarities (chloroform, acetone, and water) were selected, and solvation effects were considered using the polarized continuum model (PCM). For charged halogen-bonded complexes, the strength of the interactions tends to significantly weaken in solution, with a concomitant elongation of intermolecular distances. For neutral systems, halogen bond distances are shown to shorten and the interaction energies change slightly. Computations also reveal that in the gas phase the binding affinities decrease in the order Cl- > Br- > I-, while in solution the energy gaps of binding appear limited for the three halide anions. According to free energy results, many systems under investigation are stable in solution. Particularly, calculated free energies of formation of the complexes correlate well with halogen-bonding association constants determined experimentally. The differences of the effects of solvent upon halogen and hydrogen bonding were also elucidated. This study can establish fundamental characteristics of halogen bonding in media, which would be very helpful for applying this noncovalent interaction in medicinal chemistry and material design.