Issue 8, 2021

Developing design tools for introducing and tuning structural order in ionic liquids

Abstract

Ionic liquids (ILs) are receiving growing interest as highly tunable, multifunctional materials. Remarkably for liquids, they tend to display a high level of structural order. This structural order may even lead to the formation of mesophases such as liquid crystals (LCs). Imidazolium compounds are by far the most popular ILs, because they offer a widely versatile platform for property tuning. To investigate what is driving structural order in imidazolium-based ILs a series of asymmetrical 1-dodecyl-2-methyl-3-alkylimidazolium bromides, [C12C1Cnim][Br] with n = 0–12 have been synthesized, fully characterized and their structures and properties compared with the analogous 1-dodecyl-3-alkylimidazolium as well as the 1,2,3-triazolium bromides. The aim is to examine the influence of the replacement of the most acidic 2-H proton on the imidazolium head group by methylation on the properties and structure of ILs. For all compounds, except for compounds with butyl- and hexyl-chains as well as the protonated species, mesophase formation can be observed. Obviously, the simple presence of long alkyl chains such as dodecyl (a design concept frequently put forward in the literature) is not sufficient to support mesophase formation alone. Rather, for the formation of a liquid crystalline phase, a balance between attractive van der Waals forces, hydrogen bonds, and electrostatic interactions is required. Data from temperature-dependent small-angle X-ray scattering (SAXS) and polarizing optical microscopy (POM) suggest three different cation conformations for the studied [C12C1Cnim][Br]: cations with 0 ≤ n ≤ 4 exhibit a near-linear conformation; for 5 ≤ n ≤ 10 a V-shape is adopted, and for n = 11 or 12 a U-shape is found. We demonstrated that the structural possibility for an interdigitation of the long chains is an influential factor for the formation of a mesophase.

Graphical abstract: Developing design tools for introducing and tuning structural order in ionic liquids

Supplementary files

Article information

Article type
Paper
Submitted
18 11 2020
Accepted
08 1 2021
First published
13 1 2021
This article is Open Access
Creative Commons BY license

CrystEngComm, 2021,23, 1785-1795

Developing design tools for introducing and tuning structural order in ionic liquids

O. Renier, G. Bousrez, M. Yang, M. Hölter, B. Mallick, V. Smetana and A. Mudring, CrystEngComm, 2021, 23, 1785 DOI: 10.1039/D0CE01672A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements