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Imidazolium
Terms modified by Imidazolium Selected AbstractsImidazolium based ionic liquid crystals: structure, photophysical and thermal behaviour of [Cnmim]Br·xH2O (n = 12, 14; x=0, 1)CRYSTAL RESEARCH AND TECHNOLOGY, Issue 11 2008A. Getsis Abstract The long chain imidazolium halides [Cnmim]Br·xH2O (n = 10, 12; x = 0, 1) have been synthesized and their structural and thermal behaviour together with their photophysical properties characterized. X-ray structure analyses of the monohydrates ([C12mim]Br·H2O: triclinic, P1, no. 2, Z = 2, Pearson code aP112, a = 550.0(5) pm, b = 779.4(5) pm, c = 2296.1(5) pm, , = 81.89(5)°, , = 83.76(5)°, , = 78.102(5)°, 3523 unique reflections with Io > 2,(Io), R1 = 0.0263, wR2 = 0.0652, GooF = 1.037, T = 263(2) K; [C14mim]Br,H2O: triclinic, P1, no. 2, Z = 12, Pearson code aP11, a = 549.86(8) pm, 782.09(13) pm, c = 2511.3(4) pm, , = 94.86(2)°, , = 94.39(2)°, , = 101.83(2)°, 2063 unique reflections with Io > 2,(Io), R1 = 0.0429, wR2 = 0.0690, GooF = 0.770, T = 293(2) K) show for both compounds similar bilayered structures. Sheets composed of hydrophilic structure regions constituted by positively charged imidazolium head groups, bromide anions and hydrogen bonded water alternate with hydrophobic areas formed by interdigitated long alkyl chains belonging to imidazolium cations with different orientation. Combined differential scanning calorimetry and polarizing optical microscopy shows that the monohydrates as well as the anhydrous imidazolium salts are thermotropic liquid crystals which adopt smectic mesophases. The mesophase region is larger in case of the monohydrates when compared to the anhydrous compounds indicating that water obviously stabilizes the mesophase. All compounds show an intense whitish photoluminescence with short lived (1,,1,*) and long lived (1,,3,*) transitions. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Synthesis and Characterization of Pyrazolyl-Functionalized Imidazolium-Based Ionic Liquids and Hemilabile (Carbene)palladium(II) Complex Catalyzed Heck ReactionEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 4 2007Ruihu Wang Abstract Neat reactions of 1-(pyrazolylmethyl)imidazole with an excess of alkyl or polyfluoroalkyl halides at 100 °C followed by subsequent metathetical reactions with LiN(SO2CF3)2 or KPF6 at 25 °C gave rise to a series of monoquaternary salts 3a,3k. These salts can be also prepared through treatment of 1-alkylimidazole with 1-(chloromethyl)pyrazole hydrochloride in the presence of base, followed by anion exchange with LiN(SO2CF3)2 or KPF6. Their phase-transition temperature, thermal stability, density and solubility in common solvents have been investigated. Most of the bis(trifluoromethanesulfon)amide salts are room-temperature ionic liquids. The effect of anions and of alkyl substituents bonded to the imidazolium cation on the physicochemical properties was examined. Using 3-butyl-1-(pyrazolylmethyl)imidazolium chloride (2d), the precursor of 3-butyl-1-(pyrazolylmethyl)imidazolium bis(trifluoromethanesulfon)amide (3d), as a reactant, a hemilabile (N-heterocyclic carbene)palladium(II) complex 4 was synthesized through a (carbene)silver(I) transfer reagent. It was characterized by single-crystal X-ray diffraction analysis. The catalytic activity and recyclability of 4 in 3d were preliminarily evaluated by consecutive Heck reactions using different substrates. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Solvent Effects on the NMR Chemical Shifts of Imidazolium-Based Ionic Liquids and Cellulose ThereinMACROMOLECULAR SYMPOSIA, Issue 2 2010Stephanie Hesse-Ertelt Abstract The interactions of ionic liquids (IL) with solvents usually used in liquid-state nuclear magnetic resonance (NMR) spectroscopy are studied. The 1H- and 13C-NMR chemical shift values of 1-n-butyl-3-methyl (BM)- and 1-ethyl-3-methyl (EM)-substituted imidazolium (IM) -chlorides (Cl) and -acetates (Ac) are determined before and after diluting with deuterated solvents (DMSO-d6, D2O, CD3OD, and CDCl3). The dilution offers structural modifications of the IL due to the solvents capacity to ionization. For further investigation of highly viscous cellulose dopes made of imidazolium-based IL, solid-state NMR spectroscopy enables the reproducibility of liquid-state NMR data of pure IL. The correlation of liquid- and solid-state NMR is shown on EMIM-Ac and cellulose/EMIM-Ac dope (10 wt %). [source] Innentitelbild: Thin-Film Formation of Imidazolium-Based Conjugated Polydiacetylenes and Their Application for Sensing Anionic Surfactants (Angew. Chem.ANGEWANDTE CHEMIE, Issue 8 20108/2010) Der induzierte Blau-Rot-Übergang in Polydiacetylenen (PDAs) bildet die Grundlage für verschiedene PDA-Chemosensoren. In ihrer Zuschrift auf S.,1464,ff. beschreiben J. Yoon, J.,Y. Lee und Mitarbeiter einen tensidselektiven Sensor bestehend aus Imidazolium-PDA, der mit selektiver Verfärbung auf anionische Tenside reagiert und beispielsweise zwischen den anionischen Tensiden Natriumdodecylsulfat (SDS) und Natriumdodecylbenzolsulfonat (SDBS) unterscheiden kann. [source] Thin-Film Formation of Imidazolium-Based Conjugated Polydiacetylenes and Their Application for Sensing Anionic Surfactants,ANGEWANDTE CHEMIE, Issue 8 2010Xiaoqiang Chen Farbe bekennen: Polydiacetylen-Imidazolium-Polymere reagieren durch selektive Farbwechsel auf den Zusatz anionischer Tenside. Das System unterscheidet zudem zwischen den anionischen Tensiden Natriumdodecylsulfat (SDS) und Natriumdodecylbenzolsulfonat (SDBS). [source] ChemInform Abstract: Imidazolium-Based Polymer-Supported Gadolinium Triflate as a Heterogeneous Recyclable Lewis Acid Catalyst for Michael Additions.CHEMINFORM, Issue 35 2008Ramesh Alleti Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] An Imidazolium-Based Phosphinite Ionic Liquid (IL-OPPh2) as a Reusable Reaction Medium and PdII Ligand in Heck Reactions of Aryl Halides with Styrene and n-Butyl Acrylate.CHEMINFORM, Issue 32 2007Nasser Iranpoor Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Efficient Heck Reactions Catalyzed by a Highly Recyclable Palladium(II) Complex of a Pyridyl-Functionalized Imidazolium-Based Ionic liquid.CHEMINFORM, Issue 25 2007Ruihu Wang Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Synthesis and Characterization of Pyrazolyl-Functionalized Imidazolium-Based Ionic Liquids and Hemilabile (Carbene)palladium(II) Complex Catalyzed Heck Reaction.CHEMINFORM, Issue 18 2007Ruihu Wang Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Self-Assembly of Imidazolium-Based Rodlike Ionic Liquid Crystals: Transition from Lamellar to Micellar OrganizationCHEMISTRY - A EUROPEAN JOURNAL, Issue 15 2010Xiaohong Cheng Prof. Abstract By using aryl-amination chemistry, a series of rodlike 1-phenyl-1H -imidazole-based liquid crystals (LCs) and related imidazolium-based ionic liquid crystals (ILCs) has been prepared. The number and length of the C-terminal chains (at the noncharged end of the rodlike core) and the length of the N-terminal chain (on the imidazolium unit in the ILCs) were modified and the influence of these structural parameters on the mode of self-assembly in LC phases was investigated by polarizing microscopy, differential scanning calorimetry, and X-ray diffraction. For the single-chain imidazole derivatives nematic phases (N) and bilayer SmA2 phases were found, but upon increasing the number of alkyl chains the LC phases were lost. For the related imidazolium salts LC phases were preserved upon increasing the number and length of the C-terminal chains and in this series it leads to the phase sequence SmA,columnar (Col),micellar cubic (CubI/Pm3n). Elongation of the N-terminal chain gives the reversed sequence. Short N-terminal chains prefer an end-to-end packing of the mesogens in which these chains are separated from the C-terminal chains. Elongation of the N-terminal chain leads to a mixing of N- and C-terminal chains, which is accompanied by complete intercalation of the aromatic cores. In the smectic phases this gives rise to a transition from bilayer (SmA2) to monolayer smectic (SmA) phases. For the columnar and cubic phases the segregated end-to-end packing leads to core,shell aggregates. In this case, elongation of the N-terminal chains distorts core,shell formation and removes CubI and Col phases in favor of single-layer SmA phases. Hence, by tailoring the length of the N-terminal chain, a crossover from taper-shaped to polycatenar LC tectons was achieved, which provides a powerful tool for control of self-assembly in ILCs. [source] Comparison of Physicochemical Properties of New Ionic Liquids Based on Imidazolium, Quaternary Ammonium, and Guanidinium CationsCHEMISTRY - A EUROPEAN JOURNAL, Issue 30 2007Prashant Abstract More than 50 ionic liquids were prepared by using imidazolium, quaternary ammonium, and guanidinium cations and various anions. In these series, different cationic structures such as 1-benzyl-3-methylimidazolium [Bzmim]+, 1,3-dibenzylimidazolium [BzmiBz]+, 1-octyl-3-methylimidazolium [C8mim]+, 1-decyl-3-methylimidazolium [C10mim]+, tricapryl-methylammonium [Aliquat]+, benzyltriethylammonium [BzTEA]+, phenyltrimethylammonium [PhTMA]+, and dimethyldihexylguanidinium [DMG]+ were combined with anions, p -toluenesulfonate [TSA],, dicyanoamide [DCA],, saccharine (2-sulfobenzoic acid imide sodium salt) [SAC],, trifluoroacetate [TFA],, bis(trifluoromethanesulfonyl)imide [Tf2N],, trifluoromethanesulfonate [TfO],, and thiocyanate [SCN],. Important physical data for these ionic liquids are collated, namely solubility in common solvents, viscosity, density, melting point and water content. Apart from the viscosity, the Newtonian and non-Newtonian behavior of these ionic liquids is also disclosed. Stability of these ionic liquids under thermal, basic, acidic, nucleophilic, and oxidative conditions was also studied. The features of the solid,liquid phase transition were analyzed, namely the glass transition temperature and the heat capacity jump associated with the transition from the non-equilibrium glass to the metastable supercooled liquid. A degradation temperature of each ionic liquid was also determined. Comparisons of the properties of various ionic liquids were made. [source] Selective Extraction of Bioproducts by Ionic LiquidsCHINESE JOURNAL OF CHEMISTRY, Issue 6 2005Wang Jian-Ji Abstract Imidazolium based room temperature ionic liquids have been used to extract selectively L -tryptophan from fermentation broth. anion was found to enhance dramatically the partitioning of L -tryptophan into ionic liquid phase from aqueous solutions. [source] Acute and chronic toxicity of imidazolium-based ionic liquids on Daphnia magnaENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 1 2005Randall J. Bernot Abstract Room-temperature ionic liquids (ILs) are considered to be green chemicals that may replace volatile organic solvents currently used by industry. However, IL effects on aquatic organisms and ecosystems are currently unknown. We studied the acute effects of imidazolium-based ILs on survival of the crustacean Daphnia magna and their chronic effects on number of first-brood neonates, total number of neonates, and average brood size. Lethal concentrations of imidazolium ILs with various anions (X,) ranged from a median lethal concentration (LC50) of 8.03 to 19.91 mg L,1, whereas salts with a sodium cation (Na+ X,) were more than an order of magnitude higher (NaPF6 LC50, 9,344.81 mg L,1; NaBF4 LC50, 4765.75 mg L,1). Thus, toxicity appeared to be related to the imidazolium cation and not to the various anions (e.g., CI,, Br,, PF,6, and BF,4). The toxicity of imidazolium-based ILs is comparable to that of chemicals currently used in manufacturing and disinfection processes (e.g., ammonia and phenol), indicating that these green chemicals may be more harmful to aquatic organisms than current volatile organic solvents. We conducted 21-d chronic bioassays of individual D. magna exposed to nonlethal IL concentrations at constant food-resource levels. Daphnia magna produced significantly fewer total neonates, first-brood neonates, and average neonates when exposed to lower concentrations (0.3 mg L,1) of imidazolium-based ILs than in the presence of Na-based salts at higher concentrations (400 mg L,1). Such reductions in the reproductive output of Daphnia populations could cascade through natural freshwater ecosystems. The present study provides baseline information needed to assess the potential hazard that some ILs may pose should they be released into freshwater ecosystems. [source] Efficient Removal of Anionic Surfactants Using Mesoporous Functionalised Hybrid MaterialsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 25 2009Carmen Coll Abstract A new hybrid system for surfactant removal from water has been developed using mesoporous material (MCM-41) functionalised with suitable binding groups. Solid S1, S2 and S3 were prepared by reaction of the mesoporous material with N -methyl- N, -(propyltrimethoxysilyl)imidazolium chloride, (3-aminopropyl)trimethoxysilane or 4-[(triethoxysilylpropylthio)methyl]pyridine, respectively. The functionalised materials were characterised following standard solid-state techniques. The final prepared solids consist of a siliceous MCM-41-type mesoporous support with the surface decorated by imidazolium, amine and pyridine binding groups suitable for anion coordination. Equilibrium adsorption studies of linear alkylbenzenesulfonate (LAS) using S1, S2 and S3 in water have been carried out. The obtained adsorption data were correlated with a Langmuir isotherm model that gives an acceptable description of the experimental data. The maximum surfactant uptake/binding site (mol,mol,1) and the surfactant adsorption capacity (mmol,g,1) for materials S1, S2 and S3 were calculated. S1 shows a positive-charged functionalised surface that is independent of the pH of the solution, whereas S2 and S3 are functionalised with neutral groups that need to be protonated in order to display electrostatic binding interactions with the anionic surfactants. Therefore, whereas the adsorption capacity of S1 is pH-independent, S2 and S3 display larger LAS adsorption at acidic pH. The adsorption ability at a certain pH follows the order S1 >> S3 > S2. A remarkable maximum surfactant adsorption of 1.5 mmol per gram of material was observed for S1 at neutral pH. S2 and S3 behave as poorer adsorbents and show maximum surfactant adsorption of 0.197 and 0.335 mmol per gram of material, respectively, at pH 2.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Ratiometric Fluorescence Sensing of Fluoride Ions by an Asymmetric Bidentate Receptor Containing a Boronic Acid and Imidazolium GroupEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 18 2009Zhaochao Xu Abstract The synthesis of the first examples of anion receptors that utilize boron,fluoride interactions and (C,H)+···F, -type ionic hydrogen-bond interactions in the binding of F ions is reported herein. o -, m -, and p -Phenylboronic acids were linked to naphthoimidazolium through a methylene group. On the basis of fluorescence and 19F NMR studies, we have confirmed that the addition of fluoride to a boron center occurs prior to the formation of (C,H)+···F, -type ionic hydrogen bond with the imidazolium moiety. More importantly, these investigations have demonstrated that only the receptor bearing the ortho -directed boron and imidazolium exhibits enhanced fluoride binding. The increased binding ability of the asymmetric bidentate receptor of ortho -boronic acid and imidazolium towards F, enables it to sense fluoride ions in a 95:5 CH3CN/HEPES aqueous solution. The fluorescence responses to different anions were also explored; the ortho -boron-imidazolium receptor displayed ratiometric fluorescence changes and a high selectivity towards fluoride ions over other anions (Cl,, Br,, CH3CO2,, HSO4,, and H2PO4,).(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Synthesis and Characterization of Pyrazolyl-Functionalized Imidazolium-Based Ionic Liquids and Hemilabile (Carbene)palladium(II) Complex Catalyzed Heck ReactionEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 4 2007Ruihu Wang Abstract Neat reactions of 1-(pyrazolylmethyl)imidazole with an excess of alkyl or polyfluoroalkyl halides at 100 °C followed by subsequent metathetical reactions with LiN(SO2CF3)2 or KPF6 at 25 °C gave rise to a series of monoquaternary salts 3a,3k. These salts can be also prepared through treatment of 1-alkylimidazole with 1-(chloromethyl)pyrazole hydrochloride in the presence of base, followed by anion exchange with LiN(SO2CF3)2 or KPF6. Their phase-transition temperature, thermal stability, density and solubility in common solvents have been investigated. Most of the bis(trifluoromethanesulfon)amide salts are room-temperature ionic liquids. The effect of anions and of alkyl substituents bonded to the imidazolium cation on the physicochemical properties was examined. Using 3-butyl-1-(pyrazolylmethyl)imidazolium chloride (2d), the precursor of 3-butyl-1-(pyrazolylmethyl)imidazolium bis(trifluoromethanesulfon)amide (3d), as a reactant, a hemilabile (N-heterocyclic carbene)palladium(II) complex 4 was synthesized through a (carbene)silver(I) transfer reagent. It was characterized by single-crystal X-ray diffraction analysis. The catalytic activity and recyclability of 4 in 3d were preliminarily evaluated by consecutive Heck reactions using different substrates. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Ionic Liquids: Electropolymerization of a Bifunctional Ionic Liquid Monomer Yields an Electroactive Liquid-Crystalline Polymer (Adv. Funct.ADVANCED FUNCTIONAL MATERIALS, Issue 13 2010Mater. M. A. Firestone et al. present a polymer that incorporates an electronic component with an ionic liquid and produces a mixed ionic and electronic conductor on page 2063. Electropolymerization of a bifunctional imidazolium-based ionic liquid monomer incorporating both vinyl and thiophene groups yields a liquid-crystalline polymer that adopts an interconnected network structure formed by two orthogonally oriented lamellar sheets. The structural ordering leads to enhanced electrical conductivity. [source] Electropolymerization of a Bifunctional Ionic Liquid Monomer Yields an Electroactive Liquid-Crystalline PolymerADVANCED FUNCTIONAL MATERIALS, Issue 13 2010Sungwon Lee Abstract The preparation and polymerization of a bifunctional imidazolium-based ionic liquid (IL) monomer that incorporates both a vinyl group and a thiophene moiety is reported. Potentiodynamic electropolymerization of the monomer produces an optically birefringent polymer film that strongly adheres to the electrode surface. Fourier transform IR spectroscopy shows that polymerization occurs through both the vinyl and thienyl groups. Cylic voltammetry (CV) is used to determine the polymer oxidation potential (1.66,V) and electrochemical bandgap, Eg, of 2.45,eV. The polymer exhibits electrochromism, converting from yellow in the neutral form (,max,=,380,nm) to blue in the polaronic state at 0.6,V (,max,=,672,nm) and to blue-grey in the bipolaronic state at 1.2,V (,max,>,800,nm). Topographic atomic force microscopy (AFM) images reveal isolated (separated) fibrils. Grazing-incidence small-angle X-ray scattering (GISAXS) studies indicate a lamellar structure with a lattice spacing of 3.2,nm. Wide-angle X-ray diffraction (WAXD) studies further suggest that the polymerized thiophene sheets are oriented perpendicular to the polymerized vinylimidazolium. The electrical conductivity, as determined by four-probe dc conductivity measurements was found to be 0.53,S cm,1 in the neutral form and 2.36,S cm,1 in the iodine-doped state, values higher than typically observed for polyalkylthiophenes. The structural ordering is believed to contribute to the observed enhancement of the electrical conductivity. [source] Imidazolium Ion-Tagged Proline Organocatalyst for ,-Aminoxylation of Aldehydes and Ketones in Ionic LiquidsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1 2010Xiong Ding Abstract A novel imidazolium ion-tagged L -proline catalyst has been developed. The asymmetric ,-aminoxylation of aldehydes and ketones with excellent enantioselectivities, up to 99% ee, and high yields in ionic liquids has been achieved. The system can be easily recycled and reused for at least six times without significant loss of yields and enantioselectivity. [source] An Improved Protocol for the Direct Asymmetric Aldol Reaction in Ionic Liquids, Catalysed by Onium Ion-Tagged ProlinesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 11-12 2007Marco Lombardo Abstract Two onium ion-tagged prolines, imidazolium bis(trifluoromethylsulfonyl)imide-substituted proline 6 and butyldimethylammonium bis(trifluoromethylsulfonyl)imide-substituted proline 7, were synthesised and their catalytic activity in the direct asymmetric aldol condensation was studied in ionic liquids. For the reaction of acetone with various aldehydes, using 5,% of the catalyst, the yields of the aldols varied between 50,85,% while the ee values were in the 80,85,% range. Other ketones were studied too, the yields obtained in those cases being in the 35,78,% range while the enantioselectivities varied between 75,94,%. [source] Separation and recovery of cellulose and lignin using ionic liquids: a process for recovery from paper-based wasteJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 12 2009Huma Lateef Abstract BACKGROUND: The production of paper makes use of cellulose and lignin as a raw material, and almost all cellulose and lignin production comes from raw wood materials, contributing to deforestation and resulting in potential environmental harm. It is therefore beneficial to develop technologies for cellulose and lignin recovery for re-use and sustainability of resources. RESULTS: Three imidazolium based ionic liquids (ILs), 1-(2-cyanoethyl)-3-methylimidazolium bromide (cyanoMIMBr), 1-propyl-3-methylimidazolium bromide (propylMIMBr) and 1-butyl-3-methylimidazolium chloride (butylMIMCl), were synthesised by microwave technology and fully characterised by mass spectrometry, thermogravimetric differential scanning calorimetry, thin layer chromatography, nuclear magnetic resonance and Fourier transform infrared spectroscopies. Cellulose and lignin were soluble in all three ILs with solubility being greatest in cyanoMIMBr. Regeneration of cellulose and lignin was achieved from saturated solutions of cellulose in IL and lignin in IL for all three ILs. The ILs propylMIMBr and butylMIMBr have been used for the first time in the separation and recovery of cellulose and lignin and regeneration of the IL from a mixture of cellulose and lignin in IL. FTIR analysis confirms successful recovery. CONCLUSIONS: This work demonstrates the ability of ILs to separate and recover cellulose and lignin from a mixed system. Copyright © 2009 Society of Chemical Industry [source] Ionic liquids: solvent properties and organic reactivityJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 4 2005Cinzia Chiappe Abstract Ionic liquids are a fascinating class of novel solvents, which are attracting attention as possible ,green' alternative to volatile molecular organic solvents to be applied in catalytic and organic reactions and electrochemical and separation processes. Over 200 room temperature ionic liquids are known but for most of them physico-chemical data are incomplete or lacking. Furthermore, despite the incredible number of potential ionic liquids (evaluated as ,>,1014), generally only a few imidazolium-based salts are used in synthesis. Moreover, most of the data reported to date were focused on the effect that these new solvents have on chemical reaction products; only a few reports evidence the effect on reaction mechanisms or rate or equilibrium constants. In this review, the physico-chemical properties of the most used ionic liquids, that are relevant to synthesis, are discussed and a decided emphasis is placed on those properties that most clearly illuminate the ability of ionic liquids to affect the mechanistic aspects of some organic reactions. Copyright © 2004 John Wiley & Sons, Ltd. [source] Solvent Effects on the NMR Chemical Shifts of Imidazolium-Based Ionic Liquids and Cellulose ThereinMACROMOLECULAR SYMPOSIA, Issue 2 2010Stephanie Hesse-Ertelt Abstract The interactions of ionic liquids (IL) with solvents usually used in liquid-state nuclear magnetic resonance (NMR) spectroscopy are studied. The 1H- and 13C-NMR chemical shift values of 1-n-butyl-3-methyl (BM)- and 1-ethyl-3-methyl (EM)-substituted imidazolium (IM) -chlorides (Cl) and -acetates (Ac) are determined before and after diluting with deuterated solvents (DMSO-d6, D2O, CD3OD, and CDCl3). The dilution offers structural modifications of the IL due to the solvents capacity to ionization. For further investigation of highly viscous cellulose dopes made of imidazolium-based IL, solid-state NMR spectroscopy enables the reproducibility of liquid-state NMR data of pure IL. The correlation of liquid- and solid-state NMR is shown on EMIM-Ac and cellulose/EMIM-Ac dope (10 wt %). [source] Functionalization of nanoclays with ionic liquids for polypropylene composites,POLYMER COMPOSITES, Issue 5 2009Jin Uk Ha Cationic nanoclays were treated by ion exchange with various ionic liquids (ILs) containing cations and anions of different structure and/or molecular weight in order to investigate the effects of the IL structure and cation chain length on extent of clay dispersion, intercalation, and thermal stability. The modified clays containing imidazolium-, pyridinium-, and phosphonium-based cations were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction. Although the thermal stability of pure ILs was mostly controlled by the type of the anion present, high temperature thermal stability of the modified clays, at the IL cation loadings achieved in this work, was not significantly dependent on type, structure, or size of the cation. The latter parameters, however, were of significant importance in controlling degree of dispersion of the nanoclays during melt compounding with polypropylene (PP). Basal spacing increased proportionally to the size and type of the intercalated cations and showed little change in the PP composites. Although commercial organoclays were shown to be less thermally stable than IL modified clays, they exhibited larger basal spacing and better dispersion characteristics in the polyolefin matrix; however, they increased to the same extent the thermal stability of the PP matrix as the phosphonium modified clays. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers [source] Effect of intercalating agents on clay dispersion and thermal properties in polyethylene/montmorillonite nanocompositesPOLYMER ENGINEERING & SCIENCE, Issue 8 2008Karen Stoeffler Alkyl pyridinium, 1-vinyl alkyl imidazolium, 1,3-dialkyl imidazolium, and tetraalkyl phosphonium bromides were successfully used as intercalants for the preparation of highly thermally stable organophilic montmorillonites. Nanocomposites of linear low density polyethylene (LLDPE) and linear low density polyethylene grafted with maleic anhydride (LLDPE/LLDPE- g -MAH) were prepared from those organoclays. The micro- and nano-dispersions were analyzed through X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM): intercalation and/or partial exfoliation were found to occur only for formulations based on organoclays having an initial basal distance higher than 20 Å, suggesting the existence of a critical interfoliar distance for the delamination of silicate layers in a noninteracting polymer matrix. The properties of the nanocomposites were analyzed through differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and oscillatory rheometry. The dynamic crystallization of LLDPE was not significantly affected by the presence of clay. TGA in oxidative atmosphere proved to be very sensitive to the dispersion state of the organoclay: the thermal stability was drastically enhanced for intercalated and partially exfoliated formulations. However, the inherent thermal stability of the organoclay did not appear to influence significantly the overall thermal stability of the composite in the range of temperatures investigated (160,230°C). POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers. [source] Influence of imidazolium-based ionic liquids on the performance of ionic polymer conductor network composite actuatorsPOLYMER INTERNATIONAL, Issue 3 2010Sheng Liu Abstract We investigated the influence of ionic liquids (ILs) on the electromechanical performance of ionic polymer conductor network composite (IPCNC) actuators. Four imidazolium ILs with two cations of different sizes, i.e. 1-ethyl-3-methylimidazolium ([EMI+]) and 1-butyl-3-methylimidazolium ([BMI+]), and two anions of different sizes, i.e. tetrafluoroborate ([BF4,]) and trifluoromethanesulfonate ([Tf,]), were used. The IPCNC actuators were fabricated using a direct assembly method with RuO2/Nafion® nanocomposite as the electrode layers. The experimental results reveal that the actuator strain response time is nearly one order of magnitude shorter than the charging time. The IPCNCs with [EMI+][Tf,] exhibit the highest capacitance and the fastest response in both actuation and electrical charging as capacitors. In contrast, the IPCNCs with [EMI+][BF4,] display the slowest charging time and lowest value of capacitance as capacitors. The IPCNCs with [BMI+][BF4,] show the slowest response time. Furthermore, although the ILs used have a marked effect on the capacitances of the IPCNCs, using different ILs does not cause much change in the maximum strain of these IPCNCs. Consequently, the IPCNC actuators with [EMI+][BF4,] show the highest electromechanical conversion efficiency while those with [EMI+][Tf,] have the lowest electromechanical efficiency because of the highest capacitance and largest input electrical energy. The experimental results indicate that the two oppositely charged ions contribute in opposite manner to the strain response and hence the observed shorter actuation response time is likely caused by the strain cancellation effect between the cations and anions. Copyright © 2010 Society of Chemical Industry [source] Columnar liquid-crystalline assemblies composed of spiropyran derivatives and sulfonic acids,POLYMERS FOR ADVANCED TECHNOLOGIES, Issue 10 2008Boon-Hooi Tan Abstract A series of fan-shaped spiropyran derivatives with different length of alkyl chains has been synthesized. Liquid-crystalline (LC) assemblies of spiropyran derivatives have been formed by the addition of organic sulfonic acids such as trifluoromethylsulfonic acid, 10-camphorsulfonic acid, 4-methylbenzenesulfonic acid, and imidazolium-based ionic liquids (ILs) having a sulfonic acid group. Equimolar mixtures of a fan-shaped spiropyran derivative with the acidic imidazolium-based ILs exhibit columnar phases with wider LC temperature ranges as compared to those of other mixtures. The ionic interactions formed by the ionic imidazolium moieties should contribute to the stabilization of the columnar phases. On the other hand, equimolar mixtures of the spiropyran derivative with decane-1-sulfonic acid having a long alkyl chain and poly(4-styrenesulfonic acid) do not show mesomorphism. The chemical structure of organic sulfonic acids is a key factor for the induction and stabilization of the LC phases. Copyright © 2008 John Wiley & Sons, Ltd. [source] Three-dimensional supramolecular architecture in imidazolium hydrogen 2,3,5,6-tetrafluoroterephthalateACTA CRYSTALLOGRAPHICA SECTION C, Issue 4 2010Li-Li Yu The asymmetric unit of the title salt formed between 2,3,5,6-tetrafluoroterephthalic acid (H2tfbdc) and imidazolium (ImH), C3H5N2+·C8HF4O4,, contains one Htfbdc, anion and one ImH2+ cation, joined by a classical N,H...O hydrogen bond. The acid and base subunits are further linked by N,H...O and O,H...O hydrogen bonds into infinite two-dimensional layers with R56(32) hydrogen-bond motifs. The resulting (4,4) network layers interpenetrate to produce an interlocked three-dimensional structure. The final three-dimensional supramolecular architecture is further stabilized by the linkages of two C,H...O interactions. [source] Three-dimensional networks in bis(imidazolium) 2,2,-dithiodibenzoate and 4-methylimidazolium 2-[(2-carboxyphenyl)disulfanyl]benzoateACTA CRYSTALLOGRAPHICA SECTION C, Issue 9 2009Linheng Wei Cocrystallization of imidazole or 4-methylimidazole with 2,2,-dithiodibenzoic acid from methanol solution yields the title 2:1 and 1:1 organic salts, 2C3H5N2+·C14H10O4S22,, (I), and C4H7N2+·C14H10O4S2,, (II), respectively. Compound (I) crystallizes in the monoclinic C2/c space group with the mid-point of the S,S bond lying on a twofold axis. The component ions in (I) are linked by intermolecular N,H...O hydrogen bonds to form a two-dimensional network, which is further linked by C,H...O hydrogen bonds into a three-dimensional network. In contrast, by means of N,H...O, N,H...S and O,H...O hydrogen bonds, the component ions in (II) are linked into a tape and adjacent tapes are further linked by ,,,, C,H...O and C,H..., interactions, resulting in a three-dimensional network. [source] A two-dimensional network in the molecular salt 2-methylimidazolium hydrogen glutarate, and three-dimensional networks in the salts 2-methylimidazolium hydrogen succinate and 2-methylimidazolium hydrogen adipate monohydrateACTA CRYSTALLOGRAPHICA SECTION C, Issue 5 2009Xiang-Gao Meng All three title compounds, C4H7N2+·C4H5O4,, (I), C4H7N2+·C5H7O4,, (II), and C4H7N2+·C6H9O4,·H2O, (III), can be regarded as 1:1 organic salts. The dicarboxylic acids join through short acid bridges into infinite chains. Compound (I) crystallizes in the noncentrosymmetric Cmc21 space group and the asymmetric unit consists of a hydrogen succinate anion located on a mirror plane and a 2-methylimidazolium cation disordered across the same mirror. The other two compounds crystallize in the triclinic P space group. The carboxylic acid H atom in (II) is disordered over both ends of the anion and sits on inversion centres between adjacent anions, forming symmetric short O...H...O bridges. Two independent anions in (III) sit across inversion centres, again with the carboxylic acid H atom disordered in short O...H...O bridges. The molecules in all three compounds are linked into two-dimensional networks by combinations of imidazolium,carboxylate N+,H...O and carboxylate,carboxylate O,H...O hydrogen bonds. The two-dimensional networks are further linked into three-dimensional networks by C,H...O hydrogen bonds in (I) and by Owater,H...O hydrogen bonds in (III). According to the ,pKa rule, such 1:1 types of organic salts can be expected unambiguously. However, a 2:1 type of organic salt may be more easily obtained in (II) and (III) than in (I). [source] | |||||||||||||||||||||||||||||||