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Anions as Dynamic Probes for Ionic Liquid Mixtures.

ABSTRACT: Ionic liquid (IL) mixtures have been proposed as a viable alternative to rationally fine-tune the physicochemical properties of ILs for a variety of applications. The understanding of the effects of mixing ILs on the properties of the mixtures is however only in the very early stages. Two series of ionic liquid mixtures, based on the 1-ethyl-3-methylimidazolium and 1-dodecyl-3-methylimidazolium cations, and having a common anion (tetrafluoroborate or bis(trifluoromethylsulfonyl)imide), have been prepared and deeply characterized via multiple NMR techniques. Diffusion and relaxation methods combined with 2D ion-ion correlation (nuclear Overhauser enhancement) experiments have been used for a better understanding of the interplay between dynamics and structure of IL mixtures. A crucial role of the anion in driving the mixture's behavior emerged, making them important "dynamic probes" for gaining information of the polar and nonpolar regions of ionic liquids and their mixtures.

SUBMITTER: Di Pietro ME

PROVIDER: S-EPMC7997561 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The formation of ionic liquid (IL) mixtures has been proposed as an approach to rationally fine-tune the physicochemical properties of ILs for a variety of applications. However, the effects of forming such mixtures on the resultant properties of the liquids are only beginning to be understood. Towards a more complete understanding of both the thermodynamics of mixing ILs and the effect of mixing these liquids on their structures and physicochemical properties, the spatial arrangement and free volume of IL mixtures containing the common [C4C1im]+ cation and different anions have been systematically explored using small angle X-ray scattering (SAXS), positron annihilation lifetime spectroscopy (PALS) and 129Xe NMR techniques. Anion size has the greatest effect on the spatial arrangement of the ILs and their mixtures in terms of the size of the non-polar domains and inter-ion distances. It was found that differences in coulombic attraction between oppositely charged ions arising from the distribution of charge density amongst the atoms of the anion also significantly influences these inter-ion distances. PALS and 129Xe NMR results pertaining to the free volume of these mixtures were found to strongly correlate with each other despite the vastly different timescales of these techniques. Furthermore, the excess free volumes calculated from each of these measurements were in excellent agreement with the excess volumes of mixing measured for the IL mixtures investigated. The correspondence of these techniques indicates that the static and dynamic free volume of these liquid mixtures are strongly linked. Consequently, fluxional processes such as hydrogen bonding do not significantly contribute to the free volumes of these liquids compared to the spatial arrangement of ions arising from their size, shape and coulombic attraction. Given the relationship between free volume and transport properties such as viscosity and conductivity, these results provide a link between the structures of IL mixtures, the thermodynamics of mixing and their physicochemical properties.

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Anions as Dynamic Probes for Ionic Liquid Mixtures.

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