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Solvent Effects on the H-NMR Chemical Shifts of Imidazolium-Based Ionic Liquids.

作者信息

Du Ming-Xuan, Han Lin-Xue, Wang Shi-Rong, Xu Kuang-Jie, Zhu Wen-Rui, Qiao Xin, Liu Chen-Yang

机构信息

Department CAS Key Laboratory of Engineering Plastics, Institute of Chemistry, The Chinese Academy of Sciences, Beijing, 100190, China.

University of Chinese Academy of Sciences, Beijing, 10049, China.

出版信息

Chemphyschem. 2023 Oct 17;24(20):e202300292. doi: 10.1002/cphc.202300292. Epub 2023 Aug 10.

Abstract

The H nuclear magnetic resonance ( H-NMR) spectrum is a useful tool for characterizing the hydrogen bonding (H-bonding) interactions in ionic liquids (ILs). As the main hydrogen bond (H-bond) donor of imidazolium-based ILs, the chemical shift (δ ) of the proton in the 2-position of the imidazolium ring (H2) exhibits significant and complex solvents, concentrations and anions dependence. In the present work, based on the dielectric constants (ϵ) and Kamlet-Taft (KT) parameters of solvents, we identified that the δ are dominated by the solvents polarity and the competitive H-bonding interactions between cations and anions or solvents. Besides, the solvents effects on δ are understood by the structure of ILs in solvents: 1) In diluted solutions of inoizable solvents, ILs exist as free ions and the cations will form H-bond with solvents, resulting in δ being independent with anions but positively correlated with β . 2) In diluted solutions of non-ionzable solvents, ILs exist as contact ion-pairs (CIPs) and H2 will form H-bond with anions. Since non-ionizable solvents hardly influence the H-bonding interactions between H2 and anions, the δ are not related to β but positively correlated with β .

摘要

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