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Owing to their favorable properties, ionic liquids have recently gained recognition as possibly environmentally benign solvents. Now among the most promising industrial chemicals, they have already been labeled “green”, but this appellation seems due entirely to their very low vapor pressure. This growing interest in the various applications of ionic liquids will soon result in their presence in the environment. Therefore, reliable analytical tools for the environmental analysis of ionic liquids need to be developed urgently. This paper presents a newly developed analytical procedure for the enrichment of 1-alkyl- and 1-aryl-3-methylimidazolium ionic liquids from water samples. The method is based on cation exchange solid-phase extraction followed by selective elution. Pre-concentrated samples are subjected to high-performance liquid chromatography (HPLC) with an advanced methodology for qualitative and quantitative analysis. The overall procedure was verified by using standard spiked samples of tap water, seawater, and freshwater. [ABSTRACT FROM AUTHOR]

The present paper discusses the electrodeposition of nano-Aluminum using aromatic cation based ionic liquids. Three imidazolium chloride salts were employed, in ultrapure quality: l-ethyl-3-methyl-imidazolium chloride [EMIm]Cl, l-benzyl-3-methyl-imidazolium chloride [BzMIm]Cl and l,3-dibenzyl-imidazolium chloride [DBzIm]Cl, respectively. Anhydrous Aluminum chloride (AlCl 3 ) salt was used as a source of Aluminum ions in the ionic liquids. This research aims to achieve this goal by investigating the Aluminum coatings on gold substrate and study the effect of changing the organic cation on the properties of the resulting Al-coatings. SEM-EDAX analyses were used to determine the film composition. It was found that the particle size of the Al-deposites was dramatically reduced from the micrometer regime down to the nanometer regime with a change in the substituents of the imidazolium cations from EMIm to DBzIm, respectively. This means that the more the aromatic rings in the cation, the finer the particle size. Thickness and adhesion of the Al-deposits were decreased in the presence of the aromatic rings. [ABSTRACT FROM AUTHOR]

Description of the local microscopic structure in ionic liquids (ILs) is a prerequisite to obtain a comprehensive understanding of the influence of the nature of ions on the properties of ILs. The local structure is mainly determined by the spatial arrangement of the nearest neighboring ions. Therefore, the main interaction patterns in ILs, such as cation-anion H-bond-like motifs, cation-cation alkyl tail aggregation, and ring stacking, were considered within the framework of the nearest-neighbor approach with respect to each particular interaction site. We employed classical molecular dynamics (MD) simulations to study in detail the spatial, radial, and orientational relative distribution of ions in a set of imidazolium-based ILs, in which the 1-butyl-3-methylimidazolium (C4mim+) cation is coupled with the acetate (OAc-), chloride (Cl-), tetrafluoroborate (BF4 -), hexafluorophosphate (PF6 -), trifluoromethanesulfonate (TfO-), or bis(trifluoromethanesulfonyl)amide (TFSA-) anion. It was established that several structural properties are strongly anion-specific, while some can be treated as universally applicable to ILs, regardless of the nature of the anion. Namely, strongly basic anions, such as OAc- and Cl-, prefer to be located in the imidazolium ring plane next to the C-H2/4-5 sites. By contrast, the other four bulky and weakly coordinating anions tend to occupy positions above/below the plane. Similarly, the H-bond-like interactions involving the H² site are found to be particularly enhanced in comparison with the ones at H4-5 in the case of asymmetric and/or more basic anions (C4mimOAc, C4mimCl, C4mimTfO, and C4mimTFSA), in accordance with recent spectroscopic and theoretical findings. Other IL-specific details related to the multiple H-bond-like binding and cation stacking issues are also discussed in this paper. The secondary H-bonding of anions with the alkyl hydrogen atoms of cations as well as the cation-cation alkyl chain aggregation turned out to be poorly sensitive to the nature of the anion. [ABSTRACT FROM AUTHOR]

Supportedionic liquid membranes (SILMs) are promising tools for the separationof carbon dioxide from other gases. In this paper, new imidazolium,pyrrolidinium, piperidinium, and morpholinium ionic liquids with atriethylene glycol side chain and tosylate anions, as well as theirsymmetrical dicationic analogues, have been synthesized and incorporatedinto SILMs. The selectivities for CO2/N2andCO2/CH4separations have been measured. Theselectivities exhibited by the dicationic ionic liquids are up totwo times higher than the values of the corresponding monocationicionic liquids. Quantum chemical calculations have been used to investigatethe difference in the interaction of carbon dioxide with monocationicand dicationic ionic liquids. The reason for the increased gas separationselectivity of the dicationic ionic liquids is two-fold: (1) a decreasein permeance of nitrogen and methane through the ionic liquid layer,presumably due to their less favorable interactions with the gases,while the permeance of carbon dioxide is reduced much less; (2) anincrease in the number of interaction sites for the interactions withthe quadrupolar carbon dioxide molecules in the dicationic ionic liquids,compared to the monocationic analogues. [ABSTRACT FROM AUTHOR]

Abstract: The material known as 1-butyl-3-methylimidazolium hydroxide has been reported to be a 1:1 mixture of [BMIM]-cations and [OH]-anions and, as such, has been widely cited as a basic ionic liquid. 1,3-Disubstituted imidazolium-cations however, are prone to deprotonation at the C2-position of the imidazolium ring, a property readily exploited for the preparation of N-heterocyclic carbenes. Consequently, this reactivity may be unexpected and especially unwelcome when it leads to the decomposition of “[BMIM][OH]” itself, especially if the decomposition occurs during its use as a basic catalyst or reaction medium. Here, we highlight the putative “[BMIM][OH]”, as a case of particular inconsistency and inaccuracy in the literature and aim to dispel some of the persisting confusion surrounding its preparation, characterisation and use. The first part of this paper concerns the history, preparation and identity of so-called “[BMIM][OH]”, whilst the second part highlights some of the claimed activity, effects and problems associated with its use. Despite warnings in the literature, reports are still appearing in which mechanistic interpretations of reaction pathways and results are made without consideration of the unwanted reactivities of the 1,3-disubstituted imidazolium-cations employed. Future publications in which the use of “[BMIM][OH]” is reported should take into account the acidity of the [BMIM]-cation and the consequences this has for the chemistry being studied. [Copyright &y& Elsevier]

The terahertz and infrared frequency vibration modes of room-temperature ionic liquids with imidazolium cations and halogen anions were extensively investigated. There is an intermolecular vibrational mode between the imidazolium ring of an imidazolium cation, a halogen atomic anion with a large absorption coefficient and a broad bandwidth in the low THz frequency region (13–130 cm–1), the intramolecular vibrational modes of the alkyl-chain part of an imidazolium cation with a relatively small absorption coefficient in the mid THz frequency region (130–500 cm–1), the intramolecular skeletal vibrational modes of an imidazolium ring affected by the interaction between the imidazolium ring, and a halogen anion with a relatively large absorption coefficient in a high THz frequency region (500–670 cm–1). Interesting spectroscopic features on the interaction between imidazolium cations and halogen anions was also obtained from spectroscopic studies at IR frequencies (550–3300 cm–1). As far as the frequency of the intermolecular vibrational mode is concerned, we found the significance of the reduced mass in determining the intermolecular vibration frequency. [ABSTRACT FROM AUTHOR]

The electrochemical behavior and thermodynamic properties of Ln(III) (Ln = Eu, Sm, Dy, Nd) were studied in 1-butyl-3-methylimidazolium bromide ionic liquid (BmimBr) at a glassy carbon (GC) electrode in the range of 293–338 K. The electrode reaction of Eu(III) was found to be quasi-reversible by the cyclic voltammetry, the reactions of the other three lanthanide ions were regarded as irreversible systems. An increase of the current intensity was obtained with the temperature increase. At 293 K, the cathodic peak potentials of −0.893 V (Eu(III)), −0.596 V (Sm(III)), −0.637 V (Dy(III)) and −0.641 V (Nd(III)) were found, respectively, to be assigned to the reduction of Ln(III) to Ln(II). The diffusion coefficients (Do), the transfer coefficients (α) of Ln(III) (Ln = Eu, Sm, Dy, Nd) and the charge transfer rate constants (ks) of Eu(III) were estimated. The apparent standard potential (E0*) and the thermodynamic properties of the reduction of Eu(III) to Eu(II) were also investigated. [ABSTRACT FROM AUTHOR]

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The structure of the title compound, [Cu2(C12H24N4O2)(C3H4N2)2(CH4O)2](ClO4)2 or [Cu2(dmoxpn)(HIm)2(CH3OH)2](ClO4)2, where dmoxpn is the dianion of N, N′-bis­[3-(dimethyl­amino)prop­yl]oxamide and HIm is imidazole, consists of a centrosymmetric trans-oxamidate-bridged copper(II) binuclear cation, having an inversion centre at the mid-point of the central C—C bond, and two perchlorate anions. The CuII atom has square-pyramidal coordination geometry involving two N atoms and an O atom from the dmoxpn ligand, an N atom from an imidazole ring, and an O atom from a methanol mol­ecule. The crystal structure is stabilized by O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds and imidazole π–π stacking inter­actions to form a three-dimensional supra­molecular array. [ABSTRACT FROM AUTHOR]

In the title compound, [CuCl(C6H6N4)(H2O)][Cu(C4H5NO4)Cl]·H2O, the CuII atom in the cation is coordinated by one Cl- ion, two N atoms of the 2,2'-biimidazole ligand and one aqua ligand. Within the anion, the CuII atom is bonded to one Cl- ion, and one N and two O atoms of the iminodiacetate ligand. Neighbouring cations and anions are connected to each other by Cu···Cl semi-coordination bonds of 2.830 (12) and 3.071 (12) baring;, forming a Cu2Cl2 rectangular unit. The dinuclear units further link into a polymeric chain along the a axis through Cu···Oaqua interactions of 2.725 (3) baring;. Including the long coordination bonds, the geometries around the Cu atoms in the cation and anion are square-pyramidal and distorted octahedral, respectively. [ABSTRACT FROM AUTHOR]