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Developing design tools for introducing and tuning structural order in ionic liquids
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).ORCID iD: 0000-0002-1227-547X
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).ORCID iD: 0000-0002-0265-7431
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Number of Authors: 72021 (English)In: CrystEngComm, E-ISSN 1466-8033, Vol. 23, no 8, p. 1785-1795Article in journal (Refereed) Published
Abstract [en]

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, [C(12)C(1)C(n)im][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 [C(12)C(1)C(n)im][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.

Place, publisher, year, edition, pages
2021. Vol. 23, no 8, p. 1785-1795
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:su:diva-192320DOI: 10.1039/d0ce01672aISI: 000623435900009OAI: oai:DiVA.org:su-192320DiVA, id: diva2:1545548
Available from: 2021-04-19 Created: 2021-04-19 Last updated: 2024-07-04Bibliographically approved
In thesis
1. Exploring The Versatility Of Ionic Liquids: From fundamental understanding to materials inspired from ionic liquids
Open this publication in new window or tab >>Exploring The Versatility Of Ionic Liquids: From fundamental understanding to materials inspired from ionic liquids
2022 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Ionic liquids (ILs) have gained popularity as “green” and safe replacements for conventional organic solvents. They are defined as ionic salts displaying a melting point below 100 °C. Some of their unique characteristics also include negligible vapour pressure, good electrical conductivity as well as good thermal and chemical stability. While their “green” nature has since been disputed, they can be used and applied in many additional fields, such as solar energy production, new lighting technology and much more. 

In this thesis, the aim is to gain fundamental knowledge on ILs, specifically their structures and behaviour, in order to design materials tailored for specific applications. We also aim to use ILs to access otherwise difficult to synthesize materials and study their properties and applications.

The thermal properties of ILs are one of their most important characteristics. However, it is still poorly understood how the structural aspects of ILs influence their particular thermal behaviour. By studying different systems, we derived relationships between the structure and the thermal behaviour of ILs. Hydrogen bonding and other supramolecular interactions play a major role in controlling both the melting temperature and the IL's ability to support a liquid crystalline mesophase. This control was shown both in a series of ILs based on 1-alkyl-3-dodecylimidazolium bromide and in a series of ILs based on azobenzene-imidazolium compounds.

The stability issues associated with the electrolytes used in dye-sensitized solar cells (DSSCs) present a major disadvantage. We tested using ILs as electrolytes to avoid this problem. In our study, we used 1,3-dialkyltriazolium ILs as electrolytes in combination with the iodide redox couple, and not only was the stability of the DSSC improved but also the performance of IL-based DSSCs.

Efficient luminescent materials are always sought after. Using ILs in combination with lanthanides, we achieved highly luminescent compounds as well as some magnetic ones. ILs can also be used to access anhydrous forms of otherwise hydrophilic species, such as ions of the lanthanides. We have used acetate ILs to attain water free complexes of the ions from the whole lanthanide series, starting from the hydrated species. This simple process could be applied to more species of hydrophilic metals that are otherwise known to form hydrates.

Finally, the ligand obtained through ILs, 1,3-diethylimidazole-2-thione was used to aid in the studying of phase transitions when combined with zinc chloride (ZnCl2). It helped to reveal a yet unseen amorphous step in the solid-solid phase transition from a single crystal into another one, where morphology of the particle was preserved. I forsee that more fundamental structural studies can be conducted by forcing the coordination of the soft-donor nitrogen onto lanthanides by using dicyanamide ILs in the future.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry (MMK), Stockholm University, 2022. p. 60
Keywords
Ionic liquids, liquid crystals, DSSC, molecular design, Luminescent materials, anhydrous compounds, phase transition, complex coordination
National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-199318 (URN)978-91-7911-732-0 (ISBN)978-91-7911-733-7 (ISBN)
Public defence
2022-02-11, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B and online via Zoom, public link is available at the department website, Stockholm, 13:00 (English)
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Available from: 2022-01-19 Created: 2021-12-02 Last updated: 2022-01-18Bibliographically approved

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Renier, OlivierBousrez, GuillaumeSmetana, VolodymyrMudring, Anja-Verena

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