文献类型：期刊文献

英文题名：Noncovalent interactions in halogenated ionic liquids: theoretical study and crystallographic implications

作者：Li, Haiying[1,2];Lu, Yunxiang[1,2];Wu, Weihong[1,2];Liu, Yingtao[3];Peng, Changjun[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：2013

卷号：15

期号：12

起止页码：4405

外文期刊名：PHYSICAL CHEMISTRY CHEMICAL PHYSICS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000315411200038)】；

基金：This work was supported by the Natural Science Foundation of Shanghai (11ZR1408700), the National Natural Science Foundation of China (21103047), the National Basic Research Program of China (2009CB219902), and the Fundamental Research Funds for the Central Universities of China.

语种：英文

摘要：In recent years, several specific imidazolium-based ionic liquids with halogen substituents on the imidazole ring as well as on the alkyl chains have been reported. In this work, noncovalent interactions in four halogenated ionic liquids, i.e. 2-bromo-/iodo- and 4,5-dibromo-/diiodo-1,3-dimethylimidazolium trifluoromethanesulfonates, were systematically investigated using density functional theory calculations. The structural and energetic properties of the ion pairs for such ionic liquids have been fully examined and compared with the non-halogenated ones. It was found that C-X center dot center dot center dot O halogen bonds, C-H center dot center dot center dot O hydrogen bonds, and electrostatic interactions with the anion located over the imidazole ring in the ion pairs. In addition, the structures and energetics of two ion pairs for such ionic liquids were also explored to reproduce experimental observations. The halogen-bonded ring structures and the conformers with the concurrent C-H center dot center dot center dot O and C-X center dot center dot center dot O contacts were predicted, consistent with the X-ray crystal structures of corresponding organic salts. Finally, the implications of the observed structural and energetic features of ion pairs on the design of halogen-bonding ionic liquids were discussed. The results presented herein should provide useful information in the development of novel halogenated ionic liquids used for specific tasks ranging from organic synthesis to gas absorption.