Imidazolium Ion Research Articles

Hydrogen adsorption over Zeolite-like MOF materials modified by ion exchange

Novel porous Zeolite-like metal-organic framework (ZMOF) materials with Rho and Sod topologies are promising adsorbents for hydrogen storage due to their high surface area and, more importantly, to their capacity of being ion-exchanged, potentially changing their affinity for hydrogen. In this work, we have successfully synthesized both Rho and SodZMOF materials, optimizing experimental conditions for scaling-up the procedure already published to produce grams of material. The resultant materials were alkaline-cation-exchanged, widely characterized and finally tested as hydrogen adsorbents. RhoZMOF is converted into an amorphous phase during some of the ion-exchange processes, whereas SodZMOF, whose ion-exchange capacity has not been investigated so far, always maintains its topology for any tested exchange cation and conditions. Additionally, thermogravimetric analyses and thermal treatments followed by in-situ powder X-ray diffraction analysis have evidenced a significantly higher thermal stability of both as-prepared and ion-exchanged SodZMOF materials in comparison to their Rho-structured homologues. Moreover, the thermal stability of the cation-exchanged ZMOF samples improves when methanol is the ion-exchange solvent rather than the reported ethanol–water mixture. Nitrogen and hydrogen adsorption isotherms at 77 K suggested that alkali-exchanged materials have lower affinity for hydrogen than the as-prepared samples compensated by imidazolium ion; however, due to the smaller size of Na + or Li + cations, their lower affinity is easily compensated by the inherent increase in surface area and pore volume as exchange degree increases.

Intramolecular Cation−π Interactions As the Driving Force To Restrict the Conformation of Certain Nucleosides

Despite the well-established importance of intermolecular cation-pi interactions in molecular recognition, intramolecular cation-pi interactions have been less studied. Here we describe how the simultaneous presence of an aromatic ring at the 5'-position of an inosine derivative and a positively charged imidazolium ring in the purine base drive the conformation of the nucleoside toward a very major conformer in solution that is stabilized by an intramolecular cation-pi interaction. Therefore, the cation-pi interaction between imidazolium ions and aromatic rings can also be proposed in the design of small molecules where this type of interaction is desirable. The imidazolium ion can be obtained by a simple acidification of the pH of the media. So a simple change in pH can shift the conformational equilibrium from a random to a restricted conformation stabilized by an intramolecular cation-pi interaction. Thus the here described nucleosides can be considered as a new class of pH-dependent conformationally switchable molecules.

Arylazoimidazoliumchloride and chlorometallates: Spectroscopic and structural characterization

Protonation or dialkylation of 2-(arylazo)imidazoles (RaaiH) has generated azoimidazolium motif (RaaiH 2 +, RaaiR ′H +, RaaiR ′ 2 + where R = H, CH 3 and R ′ = Me, Et, –CH 2Ph). Electrostatic attraction between imdazolium cation and counter ions like Cl −, ZnCl 4 2 - , PtCl 6 2 - has generated hydrogen bonded azoimidazolium-chloride/chlorometallated networks. The single crystal X-ray structure of 1-benzyl-2-(phenylazo)imidazolium chloride shows tape like 1-D network of [Cl(H 2O) 4] −. Aquated Cl − forms 10 membered supracycle through hydrogen bonding with imidazolium ion. The X-ray structures of [HaaiMe 2 (1,3)] +[Me 2NH 2] + [ZnCl 4] 2− and [MeaaiH 2 +·H 2O] 2[PtCl 6] 2− show hydrogen bonded chlorometallate chain penetrated into the channel developed by organic motif. Azoimidazolium units are associated through π···π and C–H···π interactions to strengthen the supramolecular geometry.

Influence of imidazolium bis(trifluoromethylsulfonylimide)s on the rotation of spin probes comprising ionic and hydrogen bonding groups

The influence of the alkyl chain length in 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonylimide)s is studied to explore the rotation of piperidine-1-yloxyl derivatives substituted with either hydrogen bonding hydroxy group or ionic substituents, such as the cationic trimethylammonium or the anionic sulfate group placed at the 4 position. Structural variation of the ionic liquids results in differences of their viscosity influencing the rotation of the spin probes. The size of the average rotational correlation times of the spin probes dissolved in the ionic liquids depends further on the additional substituent in 4-position at these spin probes. The rotational correlation time exhibits a linear dependence on the ionic liquid viscosity in the case of the spin probe forming hydrogen bonding with the ionic liquids. In contrast to this, a deviation from the Stokes-Einstein behavior is found in the case of rotation of the charged spin probes in the 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonylimide)s substituted with a longer alkyl chain. This effect may be explained by phase separation on a molecular level between the charged part of the ionic liquid and the longer alkyl chains bound at the imidazolium ion. Although the neutral and the cationic spin probes show only a slight dependence between ionic liquid structure variation and the hyperfine coupling constants, structural effects cause changes in the hyperfine coupling constants in the case of the anionic spin probes. These probes strongly interact with the imidazolium ion.

Silaimidazolium and silaimidazolidinium ions

2-Silaimidazolium ions and 2-silaimidazolidinium ions were synthesized by Lewis acid-base adduct formation between N-heterocyclic silylenes and silyl arenium ions. They were isolated in high yields as their [B(C(6)F(5))(4)](-) salts. These salts are stable at room temperature and were characterized by NMR spectroscopy supported by the results of density functional computations of molecular structures and NMR chemical shifts. NICS calculations suggest for the imidazolium ions only a modest degree of aromaticity. Despite the bulkiness of the used substituents R(1) and R(2), silylium ions and behave as classical Lewis pairs and show no unexpected reactivity.

Ionic Liquids for Propene‐Propane Separation

AbstractThis paper presents an extensive study on the feasibility of ionic liquids (IL) for the extractive distillation of propene‐propane mixtures. A new experimental method for express screening of non‐volatile entrainers was elaborated. A series of ILs and their mixtures were screened at ambient temperature and low pressures. The screening results show that every tested IL turns a low boiler propene into a high boiler and the alkene‐to‐alkane separation factor can be as low as 0.28. The solubility and separation efficiency can be tuned by adjusting the chemical structures of the ions forming the IL. It was found that shortening of the alkyl substituents of the imidazolium ions leads to a decrease in capacity and to an increase in the separation factor. Interestingly, ILs containing nitrile functionalities in either the cation or the anion showed, in our experiments, enhanced separation ability combined with still good capacities. From our thermodynamic measurements, [EMIM][[B(CN)4] was proved to be the most promising candidate. Binary mixtures of ILs were also tested and resulted in separation factors and capacities between the values for the individual ILs. For the most promising candidates, also autoclave measurements at elevated temperatures and pressures were carried out. These experiments indicate that the separation ability decreases with growing temperature and loading. In general, our study definitely proves the high potential of ILs to act as entrainers in the extractive distillation of propene‐propane mixtures or for the separation of any other low‐boiling alkene‐alkane mixture.

2,2,6,6-Tetramethylpiperidine-1-yloxyl bound to the imidazolium ion by an acetamido group for investigation of ionic liquids

New spin probes bearing the 2,2,6,6-tetramethylpiperidine-1-yloxyl covalently bound to the imidazolium ion via a methylene spacer and an amide group are synthesized. If the anion is bis(trifluoromethylsulfonylimide) instead of iodide, the new spin probe has a similar structure as that of an ionic liquid. Nevertheless, the new spin probes are useful tools to investigate ionic liquids.

Immobilization of Phosphotungstic Acid (PTA) on Imidazole Functionalized Silica: Evidence for the Nature of PTA Binding by Solid State NMR and Reaction Studies

Phosphotungstic acid (PTA) immobilized onto imidazole functionalized fumed silica and was used as an efficient catalyst for epoxidation of a variety of olefins using aqueous H2O2 as an oxidant. Negligible leaching of PTA under the reaction conditions employed indicates a strong interaction between PTA and imidazole. The immobilized catalysts could be separated and reused after the catalytic cycle. Evidence for the heterogenization of PTA on the imidazole functionalized fumed silica has been inferred from different spectroscopic techniques like IR, UV−vis, and NMR. Importantly, the nature of binding of PTA on the support has been studied in detail by solid state NMR spectroscopy using 15N labeled imidazole support. It is clear from the NMR studies that the effective heterogenization of PTA is mainly due to imidazolium ion formation on the support by the acidic protons of PTA and the resultant ion pair.

A comparative study on different ionic liquids used as surfactants: Effect on thermal and mechanical properties of high-density polyethylene nanocomposites

Dialkyl imidazolium and alkyl phosphonium salts were synthesized to be used as new surfactants for cationic exchange of layered silicates, such as montmorillonite (MMT). The synthesized phosphonium (P-MMT) or imidazolium ion (I-MMT)-modified montmorillonites display a dramatically improved thermal degradation with respect to commonly used quaternary ammonium salts. This thermal degradation window can still be shifted toward higher temperatures after washing of modified clays. Two kinds of organic species can be identified onto clay: physically adsorbed species versus chemically adsorbed species. To evidence the impact of these thermally resistant ionic liquids, the modified montmorillonites were introduced in a great commodity polymer, i.e., high-density polyethylene. Thermoplastic nanocomposites with a very low amount of nanofillers were processed in melt by twin screw extrusion. If the thermal stability of polyethylene is slightly increased with only 2 wt.% of thermostable made clays, the stiffness–toughness compromise is well improved since a strong increase in modulus is achieved with both thermostable clays without loss of fracture properties. But these mechanical performances are mainly obtained with unwashed thermostable clays because the physically adsorbed organic species onto clay surfaces behave like a compatibilizer that helps both the dispersion into the PE matrix and improves the clay/matrix interface quality.

A quantum mechanics/molecular mechanics study of the tyrosine residue, TyrD, of Photosystem II

QM/MM calculations have been used to monitor the oxidation of the D2-Tyr160, TyrD, residue involved in redox reactions in Photosystem II. The results indicate that in the reduced form the residue is involved in hydrogen bond donation via its phenolic head group to the τ-nitrogen of the neighboring D2-His189 residue. Oxidation to form the radical is accompanied by spontaneous transfer of the phenolic hydrogen to the τ-nitrogen of D2-His189 leading to the formation of a tyrosyl-imidazolium ion complex. Deprotonation of the imidazolium ion leads to the formation of a tyrosyl-imidazole neutral hydrogen-bonded complex. Comparison of calculated and experimental hyperfine coupling tensors and g-tensors suggests that the neutral imidazole complex is formed at physiological temperatures while the imidazolium complex may be stabilized at cryogenic temperatures.

Phase Behavior of Liquid Crystals Formed in [C12mim]CI/H2O and [C12mim]CI/Alcohols Systems

Phase behaviors of different binary systems involving 1-dodecyl-3-methylimidazolium chloride ([C12mim]Cl) and H2O, [C12mim]Cl and different alcohols (1-butanol, 1-pentanol, 1-hexanol and 1-octanol) are investigated at 25 C. Hexagonal liquid crystal phase (H1) is identified in [C12mim]Cl/H2O system, and lamellar liquid-crystalline (L) phase is found in [C12mim]Cl/alcohols systems by using polarized optical microscopy and small-angle X-ray scattering techniques. The formation of such phases is considered as a synergetic result of the solvatophobic force and the hydrogen-bonded network comprising an imidazolium ring, chloride ion and water (or alcohols), which can be confirmed by Fourier transform infrared spectra. It is noticeable that in [C12mim]Cl/1-octanol system, the lattice spacings of lamellar phase increase with increasing C12mimCl concentration, which is opposite to the results of [C12mim]Cl/H2O system. This may result mainly from stronger static repulsion among hydrophilic headgroups of imidazolium salts arranged in the bilayers of lamellar structures. Further measurements by differential scanning calorimetry indicate that the lamellar phase is stable within a wide temperature range above room temperature. However, the lattice spacings decrease with the increase of temperature, which may be due to the softening of the hydrocarbon chain of [C12mim]Cl molecules. In different alcohols systems, it is found that the lamellar lyotropic liquid crystal structure is easier to be formed when the carbon chain length becomes longer.

Determination of Basic Strength of Aliphatic Amines through Ion Pair Formation in Some Ionic Liquid Solutions

To have an evaluation of the basic strength of aliphatic amines in ionic liquid solution, the stability constants relevant to the formation of amine/p-nitrophenol ion pairs were determined in different ionic liquids at 298 K. In particular, aliphatic (pyrrolidinium) and aromatic (imidazolium) ionic liquids were used. Imidazolium ions, bmim(+) and bm(2)im(+), having different hydrogen bond donor abilities were taken into account. Anions were chosen ([BF(4)(-)], [PF(6)(-)], and [NTf(2)(-)]; where NTf(2) = bis(trifluoromethansulfonyl)imide) showing different shape, size, and coordination ability. Several primary, secondary (cyclic or not), and tertiary amines were used to study the effect of amine structure on the ion pair stability. The comparison between data collected in this work and those previously obtained in ordinary molecular solvents evidence that ionic liquids are solvent media able to exalt the amine basicity. Furthermore, the experimental trends obtained in different ionic liquids can only be rationalized considering the whole of parameters affecting their tridimensional structure.

A Study of the Influence of Ionic Liquids Properties on the Kemp Elimination Reaction

The morpholino-induced elimination of 5-nitrobenzisoxazole into the relevant 2-cyano-4-nitrophenolate has been used as a sample reaction in order to investigate molecular properties of some room temperature ionic liquids. The kinetic study was carried out at 298 K by means of spectrophotometric measurements. Ionic liquids, which differ in both their cation and anion properties, were used as solvent systems. In particular, aliphatic (pyrrolidinium, piperidinium, and ammonium) and aromatic (imidazolium and pyridinium) ionic liquids were used. For aromatic cations, imidazolium ions having different hydrogen-bond donor ability or a different alkyl-chain length were taken into account. The anions chosen ([BF(4)(-)], [PF(6)(-)], [SbF(6)(-)], and [NTf(2)(-)]; where NTf(2) = bis(trifluoromethansulfonyl)imide) showed different shape, size, and coordination ability. Solvent parameters of all ionic liquids used were determined by using spectroscopic probes, such as 4-nitroaniline, N,N-diethyl-4-nitroaniline, Nile Red, and Reichardt's dye. Finally, in order to obtain information on the structural organization of the solvent systems, resonance light-scattering measurements were carried out. The collected data provide evidence that ionic liquids are solvent media which exhibit peculiar features, whose effects can be rationalized only considering all parameters affecting their three-dimensional structure.

Azoimidazolium iodocuprate(I) and iodoargentate(I)

1,3-Di-alkyl-2-(arylazo)imidazolium iodide ( RaaiR 2 ′ + I - ) has been used to prepare iodocuprate(I) and iodoargentate(I) complexes. The structural confirmation has been carried out by single crystal X-ray diffraction study in representative cases. Iodo bridged anion, [Cu 2(μ-I) 2I 2] 2−, serves as charge support to dialkylazoimidazolium ion ( RaaiR 2 ′ + ). Silver(I) compound is a trimeric iodo-bridged [Ag 3I 5] 2− that forms 1D chain while imidazolium ion, RaaiR 2 ′ + , is penetrating into the network. Electrostatic interaction between organic cation and inorganic anion and supramolecular interactions viz. hydrogen bonding, D–H–π, π–π interactions contribute to the crystal packing.

Ionic IPNs as novel candidates for highly conductive solid polymer electrolytes

AbstractFive ionic imidazolium based monomers, namely 1‐vinyl‐3‐ethylimidazolium bis(trifluoromethylsulfonyl)imide (ILM1), 1‐vinyl‐3‐(diethoxyphosphinyl)‐propylimidazolium bis(trifluoromethylsulfonyl)imide (ILM2), 1‐[2‐(2‐methyl‐acryloyloxy)‐propyl]‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (ILM3), 1‐[2‐(2‐methyl‐acryloyloxy)‐undecyl]‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (ILM4), 1‐vinyl‐3‐ethylimidazolium dicyanamide (ILM5) were prepared and used for the synthesis of linear polymeric ionic liquids (PILs), crosslinked networks with polyethyleneglycol dimethacrylate (PEGDM) and interpenetrating polymer networks (IPNs) based on polybutadiene (PB). The ionic conductivities of IPNs prepared using an in situ strategy were found to depend on the ILM nature, Tg and the ratio of the other components. Novel ionic IPNs are characterized by increased flexibility, small swelling ability in ionic liquids (ILs) along with high conductivity and preservation of mechanical stability even in a swollen state. The maximum conductivity for a pure IPN was equal to 3.6 × 10−5 S/cm at 20 °C while for IPN swollen in [1‐Me‐3‐Etim] (CN)2N σ reached 8.5 × 10−3 S/cm at 20 °C or 1.4 × 10−2 S/cm at 50 °C. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4245–4266, 2009

Oxyanion and tetrahedral intermediate stabilisation by subtilisin: Detection of a new tetrahedral adduct

The peptide-derived glyoxal inhibitor Z-Ala-Ala-Phe-glyoxal has been shown to be ∼ 10 fold more effective as an inhibitor of subtilisin than Z-Ala-Pro-Phe-glyoxal. Signals at 107.2 ppm and 200.5 ppm are observed for the glyoxal keto and aldehyde carbons of the inhibitor bound to subtilisin, showing that the glyoxal keto and aldehyde carbons are sp 3 and sp 2 hybridised respectively. The signal at 107.2 ppm from the carbon atom attached to the hemiketal oxyanion is formed in a slow exchange process that involves the dehydration of the glyoxal aldehyde carbon. Two additional signals are observed one at 108.2 ppm and the other at 90.9 ppm for the glyoxal keto and aldehyde carbons respectively at pHs 6–8 demonstrating that subtilisin forms an additional tetrahedral adduct with Z-Ala-Ala-Phe-glyoxal in which both the glyoxal keto and aldehyde carbons are sp 3 hybridised. For the first time we can quantify oxyanion stabilisation in subtilisin. We conclude that oxyanion stabilisation is more effective in subtilisin than in chymotrypsin. Using 1H-NMR we show that the binding of Z-Ala-Ala-Phe-glyoxal to subtilisin raises the p K a of the imidazolium ion of the active site histidine residue promoting oxyanion stabilisation. The mechanistic significance of these results is discussed.

Swelling of ionic and non-ionic minigels

In this paper, non-ionic poly- N-isopropylacrylamide (PNIPAM) minigels and ionic imidazolium based minigels are synthesized to study the swelling after the addition of solvent. The kinetics of swelling is described using Tanaka's model and the diffusion coefficients are calculated. They are of the same order of magnitude of those reported for macro- and microgels and far from that of water self-diffusion. The presence of charge for ionic minigels allows swelling control through the ions present in the surrounding solvent.

A Computer Simulation Model for Proton Transport in Liquid Imidazole

A multistate empirical valence bond (MS-EVB) model is developed to simulate proton transport in liquid imidazole. This approach allows proton transfer to simultaneously occur on both reaction sites (donor and acceptor) of the imidazole molecule. The underlying imidazole and imidazolium models are described by the generalized Amber force field (GAFF). The imidazole MS-EVB model was parametrized to reproduce the ab initio proton shuttling potential energy surface (PES) of a protonated imidazole dimer in the gas phase. In bulk phase at 393 K, the MS-EVB simulation yields a proton diffusion coefficient of 0.20 A(2)/ps and a Grotthuss hopping rate of 1/36 ps(-1). Both results are in good agreement with experimental results. Despite the prevalence of a classical-like imidazolium structure with highly localized protonic charge, charge delocalization is not a negligible process in the simulations. Rather, it is shown to enhance the rate of proton diffusion by approximately 40% through Grotthuss shuttling. Analysis of the EVB states reveals that the imidazolium ion's first solvation shell by imidazole molecules is highly ordered through the formation of hydrogen bonds, while the second solvation shell is highly disordered. Together with the importance of charge delocalization, this result suggests that reorientation of imidazole rings in the second solvation shell is the rate-limiting step for proton transfer.

Further investigation of the biodegradability of imidazolium ionic liquids

In continuation of our earlier investigations, this report presents a rationale behind the design of a series of imidazolium based ionic liquids and their biodegradation using the CO2 headspace test (ISO 14593 method, OECD 310). The effect on biodegradability of these salts through variation of the N-substituted side chains of imidazolium ions was examined further through incorporation of various functional groups and increased alkyl chain lengths. A series of anions containing moieties known to be biodegradable were also incorporated into a number of imidazolium based salts and examined in a similar fashion.

New ionic liquid crystals based on azobenzene moiety with two symmetric imidazolium ion group substituents

Imidazolium‐substituted azobenzene liquid crystal derivatives were synthesised and their chemical structures were determined by 1H NMR, 13C NMR and UV spectroscopy and elemental analysis. The liquid crystalline properties pf the new compounds were investigated by differential scanning calorimetry, polarising optical microscopy and powder X‐ray diffraction. The monomer DC10 was found to exhibit a monolayer smectic C (SmC) phase with schlieren texture on both heating and cooling. The effects of ionic interactions as well as the length of the alkyl chains on the mesophase are discussed. The results indicate that ionic interactions between imidazolium groups are the driving force for the formation of the monolayer SmC phase, the thermal stability of which is enhanced.