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Updated: May 28, 2026

From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding
Published on: March 24, 2018
Reaction mechanism of Cl2 and 1-alkyl-3-methylimidazolium chloride ionic liquids
Shao-Wen Hu1, Zhu-Xiang Wang, Feng Qu
1Beijing National Laboratory for Molecular Sciences, Radiochemistry and Radiation Chemistry Key Laboratory of Fundamental Science, College of Chemistry and Molecular Engineering, Peking University, Beijing, China. swhu@pku.edu.cn
Abstract:
Systems containing 1-alkyl-3-methylimidazolium chloride ionic liquid and chlorine gas were investigated. Using relativistic density functional theory, we calculated the formation mechanism of trichloride and hydrogen dichloride anions in an Emim(+)Cl(-) + Cl(2) system. Emim(+)Cl(3)(-) forms without energy barriers. The more stable species ClEmim(+)HCl(2)(-) forms through chlorine substitution. Substitution of a H on the imidazolium ring is much easier than substitution on the alkyl side chains. Infrared, Raman, ESI-MS, and (1)H NMR spectra were measured for EmimCl, BmimCl, and DmimCl with and without Cl(2) gas. The coexistence of Cl(3)(-) and HCl(2)(-), as well as chlorine-substituted cations, was confirmed by detection of their spectroscopic signals in the Cl(2) added ionic liquids. Cl substitution appears less serious for cations with longer side chains.
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