Ionic liquid crystals.

Certain concentrated mixtures of salts and solvents are not simply “solutions” anymore, but they may be described as “ionic liquids”. In this perspective paper, we describe possible criteria for the new family of ionic liquids: “solvate” ionic liquids. This subclass of ionic liquids was originally proposed by Angell et al. in their recent review; however, their criteria remain to be debated. Concentrated mixtures of lithium salts and organic solvents are useful models for these solvate ionic liquids, and the effects of the salt concentration, types of solvents, and counter anions of the lithium salts on their structure and properties have been explored to enable contrast with traditional solutions, and to help determine whether a given mixture belongs to the solvate ionic liquid or not.

https://www.rsc.org/suppdata/cp/c4/c4cp00461b/c4cp00461b1.pdf

Criteria for solvate ionic liquids

Microwave-assisted synthesis of novel imidazolium-based ionic liquid crystalline dimers

We prepared a series of binary mixtures composed of selected Na salts and glymes (tetraglyme, G4, and pentaglyme, G5) with different salt concentrations and anionic species ([X]−: [N(SO2CF3)2]− = [TFSA]−, [N(SO2F)2]− = [FSA]–, ClO4–, PF6–) and studied the effects of concentration, anionic structure, and glyme chain length on their phase diagrams and solvate structures. The phase diagrams clearly illustrate that all the mixtures form 1:1 complexes, [Na(G4 or G5)1][X]. The thermal stability of the equimolar mixtures was drastically improved in comparison with those of diluted systems, indicating that all the glyme molecules coordinate to Na+ cations to form equimolar complexes. Single-crystal X-ray crystallography revealed that [Na(G5)1][X] forms characteristic solvate structures in the crystalline state irrespective of the paired anion species. A comparison of the solvate structures of the glyme–Na complexes with those of the glyme–Li complexes suggests that the ionic radii of the coordinated alkali-metal ...

Phase Diagrams and Solvate Structures of Binary Mixtures of Glymes and Na Salts

Lanthanide-containing liquid crystals exhibiting a mesophase close to room temperature were obtained by adduct formation between a long-chain salicylaldimine Schiff base and tris(2-thenoyltrifluoroacetonato)lanthanide(III) complexes or tris(benzoyltrifluoroacetonato)lanthanide(III) complexes. The mesophase was identified as a smectic A phase. The temperature range of the mesophase was found to decrease over the lanthanide series, and no mesophase was observed for the complexes of the smallest lanthanide ions. The photoluminescence of the europium(III), samarium(III), neodymium(III), and erbium(III) complexes was studied. It is shown that the clearing point can be detected by monitoring the luminescence decay time as a function of the temperature.

Lanthanide-containing metallomesogens with low transition temperatures

The mesomorphism of hydrogen bonded complexes formed between 4'-carboxybenzo-15-crown-5 stilbazolyl ester (CBCSE) as proton acceptor and carboxylic acids as proton donors is discussed. CBCSE is a monotropic mesogen, forming a nematic phase upon quench cooling. A total of 32 hydrogen bonded complexes has been studied. Hydrogen bonding with carboxylic acids stabilizes the nematic phase, and/or induces a smectic A (SmA) phase. CBCSE forms 1:1 complexes (molar ratio) with alkanoic acids (fatty acids) and 2:1 complexes with alkanedioic acids. None of these proton donors is a mesogen itself, but the hydrogen bonded complexes are. The influence of the chain or spacer length on the transition temperatures is discussed. Besides the homologous series of the alkanoic and alkanedioic acids, the following carboxylic acids were used in this study: diglycolic acid, pyridine-2,6-dicarboxylic acid, 4-dodecyloxybenzoic acid, 3,4-bis(dodecyloxy)benzoic acid, 2,3,4-tris(dodecyloxy)benzoic acid and 3,4,5-tris(dodecyloxy)benzo...

Supramolecular liquid crystals formed by hydrogen bonding between a benzocrown-bearing stilbazole and carboxylic acids

https://lirias.kuleuven.be/bitstream/123456789/30424/1/90cholesteryl.pdf

Synthesis and thermal behaviour of lanthanide complexes of 4 '-[(cholesteryloxy)carbonyl]-benzo-15-crown-5

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Supramolecular liquid crystals formed by hydrogen bonding between a benzocrown-bearing stilbazole and carboxylic acids

Synthesis and thermal behaviour of lanthanide complexes of 4 '-[(cholesteryloxy)carbonyl]-benzo-15-crown-5