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End date: 2024 × Start date: 2020 × Start date: 2020 × DDC: 540 × Subject: Ethers × WGL Institute: INM ×

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Now showing 1 - 3 of 3
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    Anion and ether group influence in protic guanidinium ionic liquids
    (Cambridge : RSC Publ., 2023) Rauber, Daniel; Philippi, Frederik; Becker, Julian; Zapp, Josef; Morgenstern, Bernd; Kuttich, Björn; Kraus, Tobias; Hempelmann, Rolf; Hunt, Patricia; Welton, Tom; Kay, Christopher W. M.
    Ionic liquids are attractive liquid materials for many advanced applications. For targeted design, in-depth knowledge about their structure-property-relations is urgently needed. We prepared a set of novel protic ionic liquids (PILs) with a guanidinium cation with either an ether or alkyl side chain and different anions. While being a promising cation class, the available data is insufficient to guide design. We measured thermal and transport properties, nuclear magnetic resonance (NMR) spectra as well as liquid and crystalline structures supported by ab initio computations and were able to obtain a detailed insight into the influence of the anion and the ether substitution on the physical and spectroscopic properties. For the PILs, hydrogen bonding is the main interaction between cation and anion and the H-bond strength is inversely related to the proton affinity of the constituting acid and correlated to the increase of 1H and 15N chemical shifts. Using anions from acids with lower proton affinity leads to proton localization on the cation as evident from NMR spectra and self-diffusion coefficients. In contrast, proton exchange was evident in ionic liquids with triflate and trifluoroacetate anions. Using imide-type anions and ether side groups decreases glass transitions as well as fragility, and accelerated dynamics significantly. In case of the ether guanidinium ionic liquids, the conformation of the side chain adopts a curled structure as the result of dispersion interactions, while the alkyl chains prefer a linear arrangement.
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    Curled cation structures accelerate the dynamics of ionic liquids
    (Cambridge : RSC Publ., 2021) Rauber, Daniel; Philippi, Frederik; Kuttich, Björn; Becker, Julian; Kraus, Tobias; Hunt, Patricia; Welton, Tom; Hempelmann, Rolf; Kay, Christopher W.M.
    Ionic liquids are modern liquid materials with potential and actual implementation in many advanced technologies. They combine many favourable and modifiable properties but have a major inherent drawback compared to molecular liquids – slower dynamics. In previous studies we found that the dynamics of ionic liquids are significantly accelerated by the introduction of multiple ether side chains into the cations. However, the origin of the improved transport properties, whether as a result of the altered cation conformation or due to the absence of nanostructuring within the liquid as a result of the higher polarity of the ether chains, remained to be clarified. Therefore, we prepared two novel sets of methylammonium based ionic liquids; one set with three ether substituents and another set with three butyl side chains, in order to compare their dynamic properties and liquid structures. Using a range of anions, we show that the dynamics of the ether-substituted cations are systematically and distinctly accelerated. Liquefaction temperatures are lowered and fragilities increased, while at the same time cation–anion distances are slightly larger for the alkylated samples. Furthermore, pronounced liquid nanostructures were not observed. Molecular dynamics simulations demonstrate that the origin of the altered properties of the ether substituted ionic liquids is primarily due to a curled ether chain conformation, in contrast to the alkylated cations where the alkyl chains retain a linear conformation. Thus, the observed structure–property relations can be explained by changes in the geometric shape of the cations, rather than by the absence of a liquid nanostructure. Application of quantum chemical calculations to a simplified model system revealed that intramolecular hydrogen-bonding is responsible for approximately half of the stabilisation of the curled ether-cations, whereas the other half stems from non-specific long-range interactions. These findings give more detailed insights into the structure–property relations of ionic liquids and will guide the development of ionic liquids that do not suffer from slow dynamics.
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    Room temperature ionic liquids with two symmetric ions
    (Cambridge : RSC, 2023) Rauber, Daniel; Philippi, Frederik; Schroeder, Daniel; Morgenstern, Bernd; White, Andrew J. P.; Jochum, Marlon; Welton, Tom; Kay, Christopher W. M.
    Room temperature ionic liquids typically contain asymmetric organic cations. The asymmetry is thought to enhance disorder, thereby providing an entropic counter-balance to the strong, enthalpic, ionic interactions, and leading, therefore, to lower melting points. Unfortunately, the synthesis and purification of such asymmetric cations is typically more demanding. Here we introduce novel room temperature ionic liquids in which both cation and anion are formally symmetric. The chemical basis for this unprecedented behaviour is the incorporation of ether-containing side chains - which increase the configurational entropy - in the cation. Molecular dynamics simulations indicate that the ether-containing side chains transiently sample curled configurations. Our results contradict the long-standing paradigm that at least one asymmetric ion is required for ionic liquids to be molten at room temperature, and hence open up new and simpler design pathways for these remarkable materials.