Ether‐Functionalized Pyrrolidinium‐Based Room Temperature Ionic Liquids: Physicochemical Properties, Molecular Dynamics, and the Lithium Ion Coordination Environment
Ether‐Functionalized Pyrrolidinium‐Based Room Temperature Ionic Liquids: Physicochemical Properties, Molecular Dynamics, and the Lithium Ion Coordination Environment
复制标题
醚官能化吡咯烷基室温离子液体：物理化学性质、分子动力学和锂离子配位环境
DOI：
10.1002/cphc.202100380
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发表时间：
2021
期刊：
影响因子：
2.9
通讯作者：
Katayama Yasushi
中科院分区：
文献类型：
--
作者：
Yoshii Kazuki;Uto Takuya;Onishi Takakazu;Kosuga Daichi;Tachikawa Naoki;Katayama Yasushi
用实验和计算方法研究了由1-己基-1-甲基吡咯烷(吡咯1，6+)、1-丁氧甲基-1-甲基吡咯烷(吡咯1，1O4+)、1-(4-甲氧基丁基)-1-甲基吡咯烷(吡咯1，4O_1+)和1‐((2‐methoxyethoxy)methyl)‐1‐methylpyrrolidinium(吡咯1，1O_2O_1+)组成的双(三氟甲磺酸)酰胺(−)离子液体的物理化学性质。通过与吡咯1，1O4TFSA和吡咯1，4O1TFSA的比较，讨论了其物化性质与醚氧原子位置和数目的关系，并通过从头算揭示了含醚氧侧链的构象柔性。此外，分子动力学(MD)计算表明，离子分布对输运性质有很大影响。此外，我们还用拉曼光谱研究了锂离子在RTIL中的配位环境，这一结果得到了1000个离子对的MD计算的支持。所得结果将对各种应用的功能化RTIL的设计具有一定的参考价值。
The physicochemical properties of room temperature ionic liquids (RTILs) consisting of bis(trifluoromethanesulfonyl)amide (TFSA−) combined with 1‐hexyl‐1‐methylpyrrolidinium (Pyr1,6+), 1‐(butoxymethyl)‐1‐methylpyrrolidinium (Pyr1,1O4+), 1‐(4‐methoxybutyl)‐1‐methyl pyrrolidinium (Pyr1,4O1+), and 1‐((2‐methoxyethoxy)methyl)‐1‐methylpyrrolidinium (Pyr1,1O2O1+) were investigated using both experimental and computational approaches. Pyr1,1O2O1TFSA, which contains two ether oxygen atoms, showed the lowest viscosity, and the relationship between its physicochemical properties and the position and number of the ether oxygen atoms was discussed by a careful comparison with Pyr1,1O4TFSA and Pyr1,4O1TFSA.Ab initiocalculations revealed the conformational flexibility of the side chain containing the ether oxygen atoms. In addition, molecular dynamics (MD) calculations suggested that the ion distributions have a significant impact on the transport properties. Furthermore, the coordination environments of the Li ions in the RTILs were evaluated using Raman spectroscopy, which was supported by MD calculations using 1000 ion pairs. The presented results will be valuable for the design of functionalized RTILs for various applications.