文献类型：期刊文献

英文题名：Understanding of the interactions between azole-anion-based ionic liquids and 2-methyl-3-butyn-2-ol from the experimental perspective: the cage effect

作者：Fu, Xue[1];Tang, Xiaochen[1];Chen, Tingting[1];Xu, Yingjie[1,2];Luo, Xiang[1,2];Lu, Yueqing[1];Wang, Xuming[3];Qin, Dandan[3];Zhang, Lin[3]

机构：[1]Shaoxing Univ, Dept Chem, 508 Huancheng West Rd, Shaoxing 312000, Zhejiang, Peoples R China;[2]Zhejiang Engn Res Ctr Fat Soluble Vitamin, 508 Huancheng West Rd, Shaoxing 312000, Zhejiang, Peoples R China;[3]Zhejiang NHU Co Ltd, Xinchang 312500, Zhejiang, Peoples R China

年份：2022

卷号：24

期号：20

起止页码：12550

外文期刊名：PHYSICAL CHEMISTRY CHEMICAL PHYSICS

收录：SCI-EXPANDED(收录号：WOS:000796598800001)、、EI(收录号：20222412212367)、Scopus(收录号：2-s2.0-85131463273)、WOS

基金：This work was supported by the National Natural Science Foundation of China (No. 21978172) and the National Natural Science Foundation of Zhejiang Province (No. LY18B060004).

语种：英文

外文关键词：Aggregates - Light scattering - Mixtures - Negative ions

外文摘要：The interactions between azole-anion-based ionic liquids (AILs) and 2-methyl-3-butyn-2-ol (MBY) play an important role in AIL-promoted carboxylative cyclization of MBY with CO2. To better understand the interactions between AILs ([P-66614][Im], [P-66614][4-MeIm], and [P-66614][4-BrIm]) and MBY, a detailed investigation from the experimental perspective has been carried out in this study. The results show that the derivative of viscosity (eta) with the mole fraction of AIL (x(AIL)) of AIL + MBY mixtures appears to have the maximum value when x(AIL) approximate to 0.3, while H-1 NMR chemical shifts of P-CH2 of [P-66614](+) reach the minimum value at x(AIL) approximate to 0.3, indicating that [P-66614](+) of AILs tend to self-aggregate. The interaction parameters (g(ji)-g(ii)) of the systems obtained from eta by the Eyring-UNIQUAC equation are positive, and the difference between the bulk and local composition (x(i)-x(ii)) is always negative, indicating that AILs can interact with MBY. Moreover, excess molar volumes and isentropic compressibility deviations are all negative deviations and become more negative as the temperature increases, reaching a minimum value at x(AIL) approximate to 0.30, indicating that azole-based anions can form H-bonds with MBY, and MBY molecules tend to enter the aggregates formed by AILs. Consequently, the cage effect is proposed to describe the interactions between AILs and MBY: MBY first enters the cage formed by the aggregation of [P-66614](+), and then forms H-bonds with azole-based anions. Finally, the sizes of the particles of the [P-66614][Im] + MBY mixture from dynamic light scattering increase first and then decrease with x(AIL), with the maximum of 122 nm at x(AIL) approximate to 0.25, which confirms the rationality of the cage effect.