Transition-metal free ring deuteration of imidazolium ionic liquid cations

A simple, low-cost and transition-metal free ring deuteration procedure applicable to ionic liquids (ILs) with imidazolium cations has been developed. Reaction profiles for the exchange have been measured.     

Understanding the mechanism of cellulose dissolution in 1-butyl-3-methylimidazolium chloride ionic liquid via quantum chemistry calculations and molecular dynamics simulations

While N,N′-dialkylimidazolium ionic liquids (ILs) have been well-established as effective solvents for dissolution and processing of cellulose, the detailed mechanism at the molecular level still remains unclear. In this work, we present a combined quantum chemistry and molecular dynamics simulation study on how the ILs dissolve cellulose. On the basis of calculations on 1-butyl-3-methylimidazolium chloride, one of the most effective ILs dissolving cellulose, we further studied the molecular behavior of cellulose models (i.e. cellulose oligomers with degrees of polymerization n = 2, 4, and 6) in the IL, including the structural features and hydrogen bonding patterns. The collected data indicate that both chloride anions and imidazolium cations of the IL interact with the oligomer via hydrogen bonds. However, the anions occupy the first coordination shell of the oligomer, and the strength and number of hydrogen bonds and the interaction energy between anions and the oligomer are much larger than those between cations and the oligomer. It is observed that the intramolecular hydrogen bond in the oligomer is broken under the combined effect of anions and cations. The present results emphasize that the chloride anions play a critically important role and the imidazolium cations also present a remarkable contribution in the cellulose dissolution. This point of view is different from previous one that only underlines the importance of the chloride anions in the cellulose dissolution. The present results improve our understanding for the cellulose dissolution in imidazolium chloride ILs.     

Liquid phase behavior of ionic liquids with alcohols: experimental studies and modeling

Ionic liquids (ILs) have been suggested as potential "green" solvents to replace volatile organic solvents in reaction and separation processes due to their negligible vapor pressure. To develop ILs for these applications, it is important to gain a fundamental understanding of the factors that control the phase behavior of ionic liquids with other liquids. In this work, we continue our study of the effect of chemical and structural factors on the phase behavior of ionic liquids with alcohols, focusing on pyridinium ILs for comparison to imidazolium ILs from our previous studies. The impact of different alcohol and IL characteristics, including alcohol chain length, cation alkyl chain length, anion, different substituent groups on the pyridinium cation, and type of cation (pyridinium vs imidazolium) will be discussed. In general, the same type of behavior is observed for pyridinium and imidazolium ILs, with all systems studied exhibiting upper critical solution temperature behavior. The impacts of alcohol chain length, cation chain length, and anion, are the same for pyridinium ILs as those observed previously for imidazolium ILs. However, the effect of cation type on the phase behavior is dependent on the strength of the cation-anion interaction. Additionally, all systems from this study and our previous work for imidazolium ILs were modeled using the nonrandom two-liquid (NRTL) equation using two different approaches for determining the adjustable parameters. For all systems, the NRTL equation with binary interaction parameters with a linear temperature dependence provided a good fit of the experimental data.     

Surfactant ionic liquid-based microemulsions for polymerization

Surfactants based on imidazolium ionic liquids (ILs), including polymerizable surfactant ILs, have been synthesized and used to stabilize polymerizable microemulsions useful for producing polymer nanoparticles, gels, and open-cell porous materials.     

Diels-Alder reaction in protic ionic liquids

Protic imidazolium ionic liquids have been tested as reaction media in the Diels-Alder reaction between cyclopentadiene and two dienophiles (dimethyl maleate and methyl acrylate). Good conversions and endo/exo selectivities were achieved. The activation of the dienophile by hydrogen bonding with protic imidazolium ILs was demonstrated.     

Nanoclusters in ionic liquids: evidence for N-heterocyclic carbene formation from imidazolium-based ionic liquids detected by (2)H NMR

The mystery of how 1,3-substituted imidazolium-based ionic liquids (ILs) can provide high stabilization for transition-metal(0) nanoclusters, that is, in the absence of the usual strongly coordinating anions, has been probed. 2H NMR product and kinetic studies of 1,3-substituted imidazolium ILs under D2 reveal that nanocluster-catalyzed H/D exchange occurs at the 2- (as well as at the 4-, 5-, and 8-) C-H positions of the imidazolium cation. The results (i) provide compelling evidence that N-heterocyclic carbene formation and ligation of nanoclusters is occurring in ILs; and (ii) argue that N-heterocyclic carbenes merit further investigation as heretofore unappreciated stabilizers of transition-metal nanoclusters.     

Reaction of singlet oxygen with thioanisole in ionic liquid-acetonitrile binary mixtures

A study of the reaction of thioanisole with singlet oxygen in different ionic liquid-acetonitrile binary mixtures has shown that ILs are able to accelerate the thioanisole sulfoxidation when used as additives. With imidazolium ILs, the maximum efficiency is reached at x(IL) ～ 0.1-0.2, whereas for the pyrrolidinium IL a plateau is reached. These results are discussed in terms of the ILs' tendency to form ionic aggregates and of differences in sulfoxidation reaction mechanism.     

Metal-containing ionic liquids and ionic liquid crystals based on imidazolium moiety

Ionic liquids and ionic liquid crystals of imidazolium salts composed of various transition and main group metals have been reviewed. Ionic metal complexes of imidazoles and N-heterocyclic carbenes possess the similar properties were also included. These types of ILs and ILCs have been realized as potential solvents, catalysts, catalyst precursors and reagents for many organic transformations and provide ecofriendly protocols. They have also been found to play key roles in material science. Many of these IL systems are air- and moisture stable and are considered as alternatives for air- and moisture sensitive chloroaluminate-based ILs.     

On the stabilisation and surface properties of soluble transition-metal nanoparticles in non-functionalised imidazolium-based ionic liquids

Doubtless ionic liquids (ILs), particularly those based on the 1,3-dialkyl imidazolium cation, provide a flexible liquid platform to prepare, soluble and stable transition metal nanoparticles (TMNPs). ILs can act as a “solvent”, stabiliser, ligand and support for TMNPs. Soluble and stable TMNPs for specific applications can be easily prepared in ILs using a bottom-up or top-down approach. The stability of TMNPs in non-functionalised ILs is mainly related to the surface electronic stabilisation provided by protective layers of discrete supramolecular imidazolium aggregates, non-polar imidazolium alkyl side chains and NHC carbene species as well as surface hydrogen species, together with an oxide layer when present on the metal surface. The IL provides a template-like effect and does not exist as a pure double layer, rather, the IL interacts directly with the TMNP surface through both cationic and anionic species, and the non-polar groups are preferentially directed away from the surface, forming a protective layer at the interface of at least one layer thick. The main aspects involving the stabilisation, in particular the interface of TMNP surface with the ionic liquids and other species present in the media, will be presented and discussed in light of the recent experimental and theoretical results reported.     

Physicochemical properties of nitrile-functionalized ionic liquids

A series of ionic liquids (ILs) based on nitrile-functionalized imidazolium, pyridinium, and quaternary ammonium as cations and chlorides and tetrafluoroborate, hexafluorophosphate, dicyanamide, and bis(trifluoromethanesulfonyl)imide as anions have been prepared and characterized. The physicochemical properties such as spectroscopic, thermal, solubility, surface, electrochemical, tribological, and toxic properties were comparatively studied. The results showed that the incorporation of a CN group to cations could result in remarkable changes in these properties. The reason resulting in such remarkable differences in the properties may be attributed to the conformational changes in the imidazolium groups caused by the interaction between the CN group with other neighboring cations or anions and the enhancement in hydrogen-bonding interactions due to the incorporation of a CN group.     

Reversed phase liquid chromatography of alkyl-imidazolium ionic liquids

Eleven 1-alkyl-3-methyl imidazolium ionic liquid (IL) salts were analyzed in reversed phase mode with a Kromasil C18 column. The mobile phases were water-rich acetonitrile solutions (water content > or =70%, v/v) without any added salts. It is shown that it is possible to separate different ILs sharing the same cation and differing by the anion when salt-free mobile phases are used. When a buffer, acetate or phosphate salt, or any salt, such as sodium chloride or sodium tetrafluorobarate, is added to the mobile phase, the ILs differing only by their anions cannot be separated. ILs with different alkyl chains in the imidazolium cation are separated by mobile phases with or without added salts following a hydrophobic interaction behavior: log k is proportional to nC, the carbon number of the alkyl chain. Important differences in ion/stationary phase interactions are observed depending on the ionic content of the mobile phase. With salt-free mobile phases, the IL/C18 stationary phase interactions correspond to concave isotherms associated with fronting peaks for all ILs. With mobile phase containing 0.01 M of salt, tailing IL peaks correspond to convex adsorption isotherms. Also, the IL retention factor depends on the concentration and nature of the added salt. Hexafluorophosphate chaotropic anions can adsorb on the Kromasil C18 surface dramatically increasing the imidazolium cation retention factors.     

Catalytic asymmetric hydrogenation of aromatic ketones in room temperature ionic liquids

Polar bisphosphonic acid-derived Ru(BINAP)(DPEN)Cl₂ precatalysts were synthesized and immobilized in room temperature ionic liquids (RTILs) for asymmetric hydrogenation of aromatic ketones with ee values of up to 98.7%. The performance of the Ru catalysts is highly dependent on the nature of imidazolium ILs. For the imidazolium ILs without acidic protons, both ILs and Ru catalysts were recycled by simple extraction and reused. Such a simple immobilization approach also prevented the leaching of Ru (and Ru catalysts) into the chiral secondary alcohol products, and should prove desirable for the production of pharmaceutical intermediates that are free from metal contaminants.     

Redox-responsive ferrocene-containing poly(ionic liquid)s for antibacterial applications

Ferrocene(Fc)-containing imidazolium type ionic liquids(ILs) and corresponding poly(ionic liquid)(PIL) membranes with tunable antibacterial activity based on electrochemical redox reaction and host-guest chemistry were developed. The effect of Fc moiety on the antimicrobial activities against both Staphylococcus aureus(S. aureus) and Escherichia coli(E. coli) was studied by minimum inhibitory concentration(MIC). The presence of Fc groups highly enhanced the antibacterial efficiency of Fccontaining ILs because of the generation of reactive oxygen species(ROS). The electrochemical oxidation of Fc to Fc+and the formation of inclusion complexes between Fc and β-CD via host-guest interactions decreased the antibacterial activities of ILs and PIL membranes. The antibacterial activities may be recovered in some extent upon the electrochemical reduction of Fc+to Fc or the exclusion of the Fc out of the cavity of β-CD. Furthermore, all the Fc-containing PIL membranes showed relatively low hemolysis activities and none cytotoxicity toward human cells, indicating clinical feasibility in topical applications.     

Effects of Cationic Structure on Cellulose Dissolution in Ionic Liquids: A Molecular Dynamics Study

In recent years, great progress has been made in the dissolution of cellulose with ionic liquids (ILs). However, the mechanism of cellulose dissolution, especially the role the IL cation played in the dissolution process, has not been clearly understood. Herein, the mixtures of cellulose with a series of imidazolium‐based chloride ionic liquids and 1‐butyl‐3‐methyl pyridinium chloride ([C₄mpy]Cl) were simulated to study the effect that varying the heterocyclic structure and alkyl chain length of the IL cation has on the dissolution of cellulose. It was shown that the dissolution of cellulose in [C₄mpy]Cl is better than that in [C₄mim]Cl. For imidazolium‐based ILs, the shorter the alkyl chain is, the higher the solubility will be. In addition, an all‐atom force field for 1‐allyl‐3‐methyl imidazolium cation ([Amim]⁺) was developed, for the first time, to investigate the effect the electron‐withdrawing group within the alkyl chain of the IL cation has on the dissolution of cellulose. It was found that the interaction energy between [Amim]⁺ and cellulose was greater than that between [C₃mim]⁺ and cellulose, indicating that the presence of electron‐withdrawing group in alkyl chain of the cation enhanced the interaction between the cation and cellulose due to the increase of electronegativity of the cations. These findings are used to assess the cationic effect on the dissolution of cellulose in ILs. They are also expected to be important for rational design of novel ILs for efficient dissolution of cellulose.     

Liquid chromatography and characterization of ether-functionalized imidazolium ionic liquids on mixed-mode reversed-phase/cation exchange stationary phase

A new series [C_nO_mmim]Cl of imidazolium cation-based ionic liquids (ILs), with an ether functional group on the alkyl side-chain, has been prepared. The possibility of analyzing the ionic liquids by high performance liquid chromatography (HPLC) was investigated on mixed-mode reversed/cation exchange stationary phase with the aqueous-acetonitrile mobile phase. Elution parameters, such as retention factor, selectivity and column efficiency, were studied as functions of mobile phase composition and pH. The ILs were characterized by elemental analysis, and infrared, UV and ¹H, ¹³C NMR spectroscopy.     

Understanding cellulose dissolution: effect of the cation and anion structure of ionic liquids on the solubility of cellulose

The effect of ionic liquids (ILs) on the solubility of cellulose was investigated by changing their anions and cations. The structural variation included 11 kinds of cations in combination with 4 kinds of anions. The interaction between the IL and cellobiose, the repeating unit of cellulose, was clarified through nuclear magnetic resonance (NMR) spectroscopy. The reason for different dissolving capabilities of various ILs was revealed. The hydrogen bonding interaction between the IL and hydroxyl was the major force for cellulose dissolution. Both the anion and cation in the IL formed hydrogen bonds with cellulose. Anions associated with hydrogen atoms of hydroxyls, and cations favored the formation of hydrogen bonds with oxygen atoms of hydroxyls by utilizing activated protons in imidazolium ring. Weakening of either the hydrogen bonding interaction between the anion and cellulose, or that between the cation and cellulose, or both, decreases the capability of ILs to dissolve cellulose.     

Physico-chemical processes in imidazolium ionic liquids

Among the various properties exhibited by ionic liquids (ILs)--especially those based on the imidazolium cation-their inherent ionic patterns, very low vapour pressure and pronounced self-organization in the solid, liquid and even in the gas phase are particularly interesting since this allows the use of these fluids as alternative and complementary media to classical organic solvents and water in many applications. Hence, reaction paths that involve charge-separated intermediates or transition states are accelerated--by lowering the activation barrier-in the presence of ILs when compared with those performed in classical organic solvents. It is also possible, for example, to observe, by electrochemical methods, transient species (ionic and radical) that are otherwise undetectible in water or in molecular organic solvents and to investigate the interactions and behaviour of molecular, biological and macromolecular species in solution using physical and chemical methods which require special conditions such as high-vacuum, and which have been traditionally limited to solid state chemistry.     

Synthesis of chiral ionic liquids from natural amino acids

For the first time, chiral imidazolium ionic liquids containing one chiral carbon (10a-c) were synthesized from the natural amino acids by a simple and straightforward procedure. The characteristics of the chiral ILs are very similar to the popular ionic liquids.     

The initial stages of radiation damage in ionic liquids and ionic liquid-based extraction systems

Radical intermediates generated in radiolysis and photoionization of ionic liquids (ILs) composed of ammonium, phosphonium, pyrrolidinium, and imidazolium cations and bis(triflyl)amide, dicyanamide, and bis(oxalato)borate anions have been studied using magnetic resonance spectroscopy. Large yields of terminal and penultimate C-centered radicals are observed in the aliphatic chains of the phosphonium, ammonium, and pyrrolidinium cations, but not for imidazolium cation. This pattern is indicative of efficient deprotonation of a hole trapped on the parent cation (the radical dication) that competes with rapid electron transfer from a nearby anion. This charge transfer leads to the formation of stable N- or O-centered radicals; the dissociation of parent anions is a minor pathway. Addition of 10-40 wt % of trialkyl phosphate (a common extraction agent) has relatively little effect on the fragmentation of the ILs. The yield of the alkyl radical fragment generated by dissociative electron attachment to the trialkyl phosphate is <4% of the yield of the radical fragments derived from the IL solvent. The import of these observations for radiation stability of the prospective nuclear cycle extraction systems based upon the ILs is discussed.