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Mixing states of imidazolium-based ionic liquid, [C4mim][TFSI], with cycloethers studied by SANS, IR, NMR, and MD simulations

Abstract

The mixing states of imidazolium-based ionic liquid (IL), 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][TFSI]), with cycloethers, tetrahydrofuran (THF), 1,4-dioxane (1,4-DIO), and 1,3-dioxane (1,3-DIO), have been clarified on the meso- and microscopic scales using small-angle neutron scattering (SANS), IR, NMR, and molecular dynamics (MD) simulations. SANS profiles of [C4mim][TFSI]-THF-d8 and -1,4-DIO-d8 solutions at various mole fractions xML of molecular liquids (ML) have shown that [C4mim][TFSI] is heterogeneously mixed with THF and 1,4-DIO on the mesoscopic scale with a high extent in the case of the last mixture. In fact, [C4mim][TFSI] and 1,4-DIO are not miscible with each other above the 1,4-DIO mole fraction x1,4-DIO of 0.903, whereas the IL can be mixed with THF over the entire range of THF mole fraction xTHF. The results of IR and 1H and 13C NMR measurements and MD simulations showed that cycloether molecules are more strongly hydrogen-bonded with the imidazolium ring H atoms in the order of THF > 1,3-DIO > 1,4-DIO. Although 1,4-DIO and 1,3-DIO molecules are structural isomers, our results point out that 1,4-DIO cannot be strongly hydrogen-bonded with the ring H atoms. The solvation of [TFSI]- by cycloethers through the dipole-dipole interaction promote hydrogen bonding between the ring H atoms and cycloethers. Thus, 1,4-DIO with the lowest dipole moment cannot easily eliminate [TFSI]- from the imidazolium ring. It results in the weakest hydrogen bonds of 1,4-DIO with the ring H atoms. 2D-NMR of 1H{1H} rotating-frame nuclear Overhauser effect spectroscopy (ROESY) showed the interaction of the three cycloethers with the butyl group of [C4mim]+. 1,4-DIO mainly interacts with the butyl group by the dispersion force, whereas THF interacts with the IL by both hydrogen bonding and dispersion force. This leads to the higher heterogeneity of the 1,4-DIO solutions compared to the THF solutions.

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Article information


Submitted
24 Sep 2019
Accepted
09 Feb 2020
First published
10 Feb 2020

Phys. Chem. Chem. Phys., 2020, Accepted Manuscript
Article type
Paper

Mixing states of imidazolium-based ionic liquid, [C4mim][TFSI], with cycloethers studied by SANS, IR, NMR, and MD simulations

M. Kawano, K. Sadakane, H. Iwase, M. Matsugami, B. A. MAREKHA, A. Idrissi and T. Takamuku, Phys. Chem. Chem. Phys., 2020, Accepted Manuscript , DOI: 10.1039/C9CP05258E

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