文献类型：期刊文献

英文题名：The Interactions between Imidazolium-Based Ionic Liquids and Stable Nitroxide Radical Species: A Theoretical Study

作者：Zhang, Shaoze[1,2];Wang, Guimin[3,4];Lu, Yunxiang[1,2];Zhu, Weiliang[3,4];Peng, Changjun[1,2];Liu, Honglai[1,2]

机构：[1]East China Univ Sci & Technol, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[3]Chinese Acad Sci, Shanghai Inst Mat Med, Drug Discovery & Design Ctr, Shanghai 201203, Peoples R China;[4]Univ Chinese Acad Sci, 19A Yuquan Rd, Beijing 100049, Peoples R China

年份：2016

卷号：120

期号：30

起止页码：6089

外文期刊名：JOURNAL OF PHYSICAL CHEMISTRY A

收录：;EI(收录号：20163202703187);WOS:【SCI-EXPANDED(收录号:WOS:000381236200015)】；

基金：This work was supported by the National Basic Research Program of China (2015CB251401), the National Natural Science Foundation of China (21473054), and the Fundamental Research Funds for the Central Universities of China.

语种：英文

外文关键词：Hydrogen bonds - Ions - Density functional theory - Density of liquids

摘要：In this work, the interactions between imidazolium-based ionic liquids and some stable radicals based on 2,2,6,6-tetramethylpiperidine-1-yloxyl (TEMPO) have been systematically investigated using density functional theory calculations at the level of M06-2x. Several different substitutions, such as hydrogen. bonding forrnation substituent (OH) and ionic substituents (N(CH3)(3)(+) and OSO3-), are presented at the 4-position of the spin probe, which leads to additional hydrogen bonds or ionic interactions between these substitutions and ionic liquids. The interactions in the systems of the radicals containing ionic substitutions with ionic liquids are predicted much stronger than those in the systems of neutral radicals, resulting in a significant reduction of the mobility of ionic radicals in ionic liquids. To further understand the nature of these interactions, the natural bond order, atoms in molecules, noncovalent interaction index, electron density difference, energy decomposition analysis, and charge decomposition analysis schemes were employed. The additional ionic interactions between ionic radicals and counterions in ionic liquids are dominantly contributed from the electrostatic term, while the orbital interaction plays a major role in other interactions. The results reported herein are important to understand radical processes ionic liquids and will be very useful in the design of task-specific ionic liquids to make the processes more efficient.