TY - JOUR
T1 - Ether-Functionalized Pyrrolidinium-Based Room Temperature Ionic Liquids
T2 - Physicochemical Properties, Molecular Dynamics, and the Lithium Ion Coordination Environment
AU - Yoshii, Kazuki
AU - Uto, Takuya
AU - Onishi, Takakazu
AU - Kosuga, Daichi
AU - Tachikawa, Naoki
AU - Katayama, Yasushi
N1 - Funding Information:
Part of this research was supported by the Japan Society for the Promotion of Science (JSPS KAKENHI Grant Numbers 19K15686). The QM and MD calculations were partly carried out using the computer resource offered under the category of Intensively Promoted Projects by Research Institute for Information Technology, Kyushu University.
Funding Information:
Part of this research was supported by the Japan Society for the Promotion of Science (JSPS KAKENHI Grant Numbers 19K15686). The QM and MD calculations were partly carried out using the computer resource offered under the category of Intensively Promoted Projects by Research Institute for Information Technology, Kyushu University.
Publisher Copyright:
© 2021 Wiley-VCH GmbH
PY - 2021/8/4
Y1 - 2021/8/4
N2 - 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 initio calculations 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.
AB - 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 initio calculations 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.
KW - Raman spectroscopy
KW - ionic liquids
KW - molecular dynamics
KW - physicochemical properties
KW - viscosity
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U2 - 10.1002/cphc.202100380
DO - 10.1002/cphc.202100380
M3 - Article
C2 - 34129270
AN - SCOPUS:85109163931
SN - 1439-4235
VL - 22
SP - 1584
EP - 1594
JO - ChemPhysChem
JF - ChemPhysChem
IS - 15
ER -