Crystallography of Ionic Liquids

Winterton, N.

doi:10.1002/9781118840061.ch11

Cited by 7 publications

(13 citation statements)

References 750 publications

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“…While IL chemists mostly rely on computational approaches to gain an enhanced understanding of intermolecular interactions within IL systems and the conformational states of each component of the salt, it is noteworthy that comparable methods taking advantage of crystallographic studies have been scarcely addressed . Herein, we expand upon our previous works on TPP-derived ionic materials by reporting the synthesis and characterization of four TPP-based ILs containing perfluoroalkyl anions (Figure ).…”

Section: Introductionmentioning

confidence: 99%

Developing Structural First Principles for Alkylated Triphenylphosphonium-Based Ionic Liquids

et al. 2021

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While ionic liquids have proved to be versatile materials for a wide spectrum of applications, e.g., energy, materials, and medicine, several challenges remain concerning the rational design of novel materials. In light of this, a series of four triphenylphosphonium-based ionic liquids have been synthesized for the first time. These compounds exhibit high thermal stability with decomposition temperatures up to 450 °C. Their solid-state structures are characterized by single-crystal X-ray diffraction and the intermolecular interactions rigorously analyzed via Hirshfeld surface analysis. It was found that the unique geometries of the anions used in the study form distinct interactions with the cations. The interactions in the crystalline state are correlated with the thermal properties of the four ionic liquids to rationalize the melting points and phase transitions for each compound. The observed arrangements of the alkyl chains on the cations are investigated computationally to gain an understanding of how rotational freedom may impact the thermal properties of the compounds. By intention, each IL reported in this work offers a unique property profile and contributes to the ever-growing ionic liquid catalog.

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Section: Introductionmentioning

confidence: 99%

Developing Structural First Principles for Alkylated Triphenylphosphonium-Based Ionic Liquids

et al. 2021

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“…For example, we recently showed that the N -butyl- N -methylpyrrolidinium cation can adopt multiple conformations which separately stabilize different tautomers of the [B 9 H 14 ] − anion in the same crystal structure . However, despite the fact that a vast range of ILs with such cations have been structurally characterized, there are surprisingly few sets of related structures which could be used to precisely identify structural consequences of using tetraalkylammonium and phosphonium cations …”

mentioning

confidence: 99%

“…9 However, despite the fact that a vast range of ILs with such cations have been structurally characterized, there are surprisingly few sets of related structures which could be used to precisely identify structural consequences of using tetraalkylammonium and phosphonium cations. 10 Here, we have selected two structurally similar, biologically active anions both derived from benzoic acids (Scheme incorporated in a number of ILs. 11−14 [Dic] − is the conjugate base of 3,6-dichloro-2-methoxybenzoic acid and one of the most widely used agrochemicals, which researchers worldwide including our group have incorporated into ILs to improve uptake into plants and reduce environmental drift.…”

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confidence: 99%

Can Melting Point Trends Help Us Develop New Tools To Control the Crystal Packing of Weakly Interacting Ions?

Mishra

Kelley

Shamshina

et al. 2018

Crystal Growth & Design

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Ionic liquid forms of biologically active molecules (e.g., active pharmaceutical ingredients or herbicides) are often designed by using weakly interacting, conformationally flexible ions. However, crystalline forms of these molecules involve strong interactions and efficient packing. The salts of biologically active molecules may completely lack the directional supramolecular synthons typically used in crystal engineering, and thus new tools must be developed to control the crystal packing without strong directional interactions and predict their structure−property relationships in advance. The crystal structures of tetrabutylammonium and phosphonium salts of two structurally related, biologically active ions, salicylate and dicamba, show systematic differences from their free acids and metal salts, which are dominated by strong directional interactions. Molecular conformation and the structure of oligomeric ions of acids and their conjugate bases are conserved across multiple structures. The use of flexible, weakly coordinating cations to make salts of high melting biologically active acids can dramatically change melting points based on the size and shape complementarity of the ions and the ability of the cations to enhance anion−anion repulsion.

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“…4,20–22 Analysis of the crystal structures of ILs can offer a wealth of knowledge, in particular with regards to cation–cation, cation-anion, and anion–anion interactions. 23–25 Evaluation and quantification of the non-covalent interactions in ILs promotes the development of models useful in the prediction of novel materials. 5,6 Studies on single crystals of long-alkyl chain bearing ILs is particularly challenging, however, given the difficulties in crystal growth coupled with the complex thermal behavior of the molecules.…”

Section: Introductionmentioning

confidence: 99%

“…26 Specifically, long-alkyl chains tend to disrupt, or at least weaken, lattice formation due to many accessible conformations and geometries of the chains, slowing phase transitions such as crystallization. 23,27 Further, slow crystallization kinetics also play a role in the difficulties with single-crystal formation of these class of ILs. Despite these challenges, however, crystallography has played a key role in the development of this field.…”

Section: Introductionmentioning

confidence: 99%

Bridging the crystal and solution structure of a series of lipid-inspired ionic liquids

et al. 2023

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Crystallography of Ionic Liquids

Cited by 7 publications

References 750 publications

Developing Structural First Principles for Alkylated Triphenylphosphonium-Based Ionic Liquids

Developing Structural First Principles for Alkylated Triphenylphosphonium-Based Ionic Liquids

Can Melting Point Trends Help Us Develop New Tools To Control the Crystal Packing of Weakly Interacting Ions?

Bridging the crystal and solution structure of a series of lipid-inspired ionic liquids

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