J. Appl. Cryst.の発刊に際して

This Review covers the recent developments (2005-2015) in the design, synthesis, characterization, and application of thermotropic ionic liquid crystals. It was designed to give a comprehensive overview of the "state-of-the-art" in the field. The discussion is focused on low molar mass and dendrimeric thermotropic ionic mesogens, as well as selected metal-containing compounds (metallomesogens), but some references to polymeric and/or lyotropic ionic liquid crystals and particularly to ionic liquids will also be provided. Although zwitterionic and mesoionic mesogens are also treated to some extent, emphasis will be directed toward liquid-crystalline materials consisting of organic cations and organic/inorganic anions that are not covalently bound but interact via electrostatic and other noncovalent interactions.

Ionic Liquid Crystals: Versatile Materials.

Ionic liquids are solvents that consist entirely of ions. These nonvolatile and nonflammable solvents offer interesting opportunities for lanthanide and actinide chemistry. They can replace the organic phase in solvent extraction systems and can be used as nonaqueous electrolytes for electrodeposition of metals. Ionic liquids could find applications in the nuclear fuel cycle. Lanthanide coordination compounds or lanthanide-containing nanoparticles can be obtained via ionothermal or microwave-assisted synthesis in ionic liquids. Lanthanide-doped ionogels are a new type of luminescent hybrid materials. Ionic liquids can serve as solvents for lanthanide-mediated organic reactions, and there are several examples of high reactivity and selectivity.

Lanthanides and Actinides in Ionic Liquids

Ionic liquids with chlorometallate anions may not have been the first ionic liquids, however, it was their development that lead to the recognition that ionic liquids are a distinct, and useful, class of (functional) materials. While much of the phenomenal interest and attention over the past two decades has focussed on ‘air and water stable’ ionic liquids, research and application of chlorometallate systems has continued unabated albeit largely out of the main spotlight. The defining characteristic of chlorometallates is the presence of complex anionic equilibria, which depend both on the type and on the concentration of metal present, and leads directly to their characteristic and individual properties. Here, we review the experimental techniques that can be applied to study and characterise the anion speciation in these ionic liquids and, using recent examples, illustrate how their applications base is evolving beyond traditional applications in Lewis acidic catalysis and electrochemistry through to uses as soft and component materials, in the ionothermal synthesis of semiconductors, gas storage systems and key components in the development of biomass processing.

/pdf/halometallate-ionic-liquids-revisited-148valrncm.pdf

Halometallate ionic liquids--revisited.

Binary mixtures of the ionic liquid betainium bis(trifluoromethylsulfonyl)imide and water show an upper critical solution temperature. This solvent system has been used to extract metal ions by phase-transition extraction, using zwitterionic betaine as extractant. The system is efficient for the extraction of trivalent rare-earth, indium and gallium ions. This new type of metal extraction system avoids problems associated with the use of viscous ionic liquids, namely, the difficulty of intense mixing of the aqueous and ionic liquid phases by stirring.

Homogeneous Liquid–Liquid Extraction of Metal Ions with a Functionalized Ionic Liquid

A series of nitrile-functionalized ionic liquids were found to exhibit temperature-dependent miscibility (thermomorphism) with the lower alcohols. Their coordinating abilities toward cobalt(II) ions were investigated through the dissolution process of cobalt(II) bis(trinfluoromethylsulfonyl)-imide and were found to depend on the donor abilities of the nitrile group. The crystal structures of the cobalt(II) solvates [Co(C(1)C(1CN)Pyr)(2)(Tf(2)N)(4)] and [Co(C(1)C(2CN)Pyr)(6)][Tf(2)N](s). which were isolated from ionic-liquid solutions. gave in insight into the coordination chemistry of functionalized ionic liquids. Smooth layers of cobalt metal could be obtained by electrodeposition of the cobalt-containing ionic liquids.

Cobalt(II) complexes of nitrile-functionalized ionic liquids

The crystal structure of the title compound, (C6H11N2)3[EuBr6], consists of 1-ethyl-3-methyl­imidazolium cations and centrosymmetric octa­hedral hexa­bromido­europate anions. The [EuBr6]3− anions are located at the corners and face-centres of the monoclinic unit cell. Characteristic hydrogen-bonding inter­actions can be observed between the bromide anions and the acidic H atoms of the imidazolium cations.

/pdf/tris-1-ethyl-3-methylimidazolium-hexabromidoeuropate-iii-3kdrpegks0.pdf

Tris(1-ethyl-3-methylimidazolium) hexabromidoeuropate(III)

Six ionic liquids based on the 1-butyl-3-methylimidazolium cation have been studied. As anions Cl−, Br−, I−, [NCS]−, [N(CN)2]−, and [BF4]− were selected. The electrical conductivities were determined between 173 and 393 K based on impedance measurements in the frequency range from 0.1 to 107 Hz. The electrical conductivity increases, whereas the glass transition temperature, the fragility, and the low temperature activation energy decrease with increasing anion size. The results can be understood from the changing anion-cation interaction strength with changing anion size and from the energy landscape interpretation of the glass transition dynamics.

Influence of the anion on the electrical conductivity and glass formation of 1-butyl-3-methylimidazolium ionic liquids

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Cobalt(II) complexes of nitrile-functionalized ionic liquids

Tris(1-ethyl-3-methylimidazolium) hexabromidoeuropate(III)

Influence of the anion on the electrical conductivity and glass formation of 1-butyl-3-methylimidazolium ionic liquids