- Structural factors to improve physico-chemical properties of zwitterions as ion conductive matrices
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Thermal properties and ion conductive characteristics of equimolar mixtures of zwitterion and lithium salts (Z/L mixtures) have been investigated. Through a systematic study of their structure-property relationship, we describe a zwitterion structure that produces high ionic conductivity when the zwitterion is mixed with lithium salt. We found that a pure zwitterion containing imide anion melted at 87 °C and the melting point of pure zwitterions was lowered in proportion to the alkyl spacer chain length between the anion and cation sites. In Z/L mixtures, ionic liquid-like domain formed between the cation sites of zwitterions and the anions of lithium salts regardless of the anion structure of the zwitterions. However, the anion structure affected the transference number of the lithium cation in the Z/L mixtures. To improve the thermal stability and the ionic conductivity of Z/L mixtures, suitable alkyl chain length between the cation and anion sites was determined to be 5 to 7 CH2 units. The Royal Society of Chemistry 2006.
- Narita, Asako,Shibayama, Wataru,Ohno, Hiroyuki
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- The electrochemical synthesis of polycationic clusters
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As a new method for the synthesis of chalcogen polycationic clusters, the electrochemical dissolution of elemental tellurium in ionic liquids (IL) or in liquid SO2 is presented. ILs used are ethylmethylimidazolium triflate [OTf]- and tetraalkylammonium triflylimide [NTf2]-. Tristriflylmethanide [CTf3]- was used as [BuMeIm][CTf3] as the electrolyte in SO2. This allowed for the isolation of [Te4][CTf3]2, [Te6][OTf]4, and [Te8][NTf2]2 containing the square [Te4]2+, the prismatic [Te6]4+, and the novel barrelane-shaped [Te8]2+. The compounds are novel compositions as they do not contain the usual halometalate anions, but rather common weakly coordinating anions. The 125Te NMR spectrum of an IL solution containing [Te8]2+ features only one broad signal at 2700 ppm. DFT calculations show that slight concerted displacements within the [Te8]2+ cluster lead to a fluxional molecular structure and a fast valence isomerism with a very low activation barrier of about 8 kJ mol-1. Anodic oxidation of elemental tellurium in ionic liquids provides access to the polycationic clusters [Te4]2+, [Te6]4+, and the new cluster [Te8]2+ with a barrelane structure (see picture). The characterization of the [Te8]2+ ion by 125Te NMR spectroscopy in solution showed a dynamic molecule with fast valence isomerism.
- Schulz, Christopher,Daniels, J?rg,Bredow, Thomas,Beck, Johannes
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- Ionothermal synthesis of new cobalt and chromium thiophosphate anions [Co(Co(P3S8)2)2]4- and [Cr(P3S9)2]3-
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Two new metal thiophosphate anions, [Co(Co(P3S8)2)2]4- and [Cr(P3S9)2]3-, have been isolated as single crystals of EMIM (1-ethyl-3-methylimidazolium) salts from ionothermal reaction of the elements in [EMIM][CF3SO3]. The former compound is structurally unique from known thiophosphate anions, contains three cobalt ions in two different coordination environments and oxidation states, and has bridging, polydentate P3S83- groups that coordinate to the cobalt ions through both S and P ions. The chromium thiophosphate anion contains octahedrally-coordinated Cr ions and is structurally similar to the known ion [Ni(P3S9)2]4-. The structures of both salts were determined by single-crystal X-ray diffraction. Both compounds were characterized by EDX and IR spectroscopies.
- Cody, Jason A.,Dalecky, Lauren M.,Juillerat, Christian A.,Alexander, Grant C.B.,Shylanski, Luke C.
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- The Volumetric and Transport Properties of 1-Ethyl-3-Methylimidazolium Trifluoromethanesulfonate Ionic Liquid and Propylene Carbonate Binary System
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In the present work, a new binary mixture system composed of the ionic liquid 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([Emim][CF3SO3]) and propylene carbonate (PC) was prepared. The densities, dynamic viscosities, and electrical conductivities of ([Emim][CF3SO3] + PC) were measured over the whole concentration range (mole fractions of IL from 0 to 1) for temperatures from 288.15 to 353.15?K. The excess molar volumes (VE) and viscosity deviations (Δη) of the binary systems were calculated to characterize the volume contraction and intermolecular interactions in the mixture system, and both were correlated with the Redlich–Kister polynomial equation. The Vogel–Fulcher–Tamman equation was used to describe the temperature dependences of the dynamic viscosities and the electrical conductivities of the binary system. Further, density functional theory calculations were employed to obtain the structure, energy, and COSMO charge distributions of the cation and anion of the IL and the PC molecule, and the intermolecular interactions in the binary mixture system were evaluated.
- Wei, Ying,Zhang, Wenbo,Zhang, Xinyuan,Yang, Huige,Zhang, Qingguo
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- A sequential one-pot strategy for the synthesis of triterpenoid saponins in ionic liquid [emim][otf]
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1-Ethyl-3-methylimidazolium trifluoromethanesulfonate ([emim][OTf]) is an efficient co-solvent and co-promoter for one-pot sequential glycosylation with the combined use of thioglycosides and trichloroacetimidates (or N-phenyltrifluoroacetimidates) donors
- Song, Yiming,Guo, Tiantian,Liu, Qingchao,Song, Weiguo,Li, Fahui
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- High conversion, solvent free, continuous synthesis of imidazolium ionic liquids in spinning tube-in-tube reactors
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A spinning tube-in-tube (STT) reactor has been used for the accelerated solvent-free synthesis of a number of l-methylimidazole-based ionic liquids with excellent conversions (>99%) and high throughputs (tens of kg/day).
- Gonzalez, Michael A.,Ciszewski, James T.
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- ZnO Nanoparticle Formation from the Molecular Precursor [MeZnOtBu]4by Ozone Treatment in Ionic Liquids: in-situ Vibrational Spectroscopy in an Ultrahigh Vacuum Environment
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As reported previously, novel ZnO nanostructures can be grown by oxidation of [MeZnOtBu]4“building blocks” with O3in ionic liquids (ILs). In this study, we have explored the role of the IL during ZnO formation by in-situ infrared reflection absorption spectroscopy (IRAS) in ultrahigh vacuum (UHV). [MeZnOtBu]4and [C2C1Im][OTf] were (co-)deposited as thin films by physical vapor deposition (PVD) onto Au(111), separately or simultaneously. The IR spectrum of [MeZnOtBu]4was analyzed between 300 and 4000 cm–1based on calculated spectra from density-functional theory (DFT). Spectral changes in the IL-related bands during the thermal treatment of [MeZnOtBu]4in [C2C1Im][OTf] indicate the loss of the precursor ligands and the interaction of the IL with the growing ZnO aggregates. The films were treated with ozone (10–6mbar) in UHV and the spectral changes were monitored in-situ by IRAS. Slow ozonolysis of [C2C1Im][OTf] is observed. Spectroscopically we identify the primary ozonide formed by addition of O3to [C2C1Im]+and suggest a reaction mechanism, which leads to a biuret derivative. Upon ozone treatment of mixed [MeZnOtBu]4/[C2C1Im][OTf] films, ZnO aggregates are formed at the IL/vacuum interface. Ozonolysis of [C2C1Im][OTf] is suppressed. Upon annealing to 320 K, further ZnO aggregates are formed, leading to enclosure of [C2C1Im][OTf] in the ZnO film. At 380 K the IL is released from the mixed film. The pure [C2C1Im][OTf] desorbs at 420 K, leaving behind the ZnO phase.
- Bauer, Tanja,Voggenreiter, Markus,Xu, Tao,W?hler, Tobias,Agel, Friederike,Pohako-Esko, Kaija,Schulz, Peter,D?pper, Tibor,G?rling, Andreas,Polarz, Sebastian,Wasserscheid, Peter,Libuda, J?rg
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- Induction of lignin solubility for a series of polar ionic liquids by the addition of a small amount of water
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Addition of a small amount of water was found to induce the lignin solubilizing ability in several polar ionic liquids which showed no lignin solubility in the absence of water. Similarly, addition of water was found to enhance lignin solubility in many polar ionic liquids. Though addition of water lowered the proton accepting ability of these ionic liquids, their proton donating ability was found to increase. The lignin dissolution by ionic liquids was newly found to be a function of both the proton accepting ability and proton donating ability of the ionic liquids. Water is a poor solvent for polysaccharides, and water addition has therefore been confirmed to be effective to improve the selective extraction yield of lignin from cedar powder under mild conditions.
- Akiba, Takashi,Tsurumaki, Akiko,Ohno, Hiroyuki
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supporting information
p. 2260 - 2265
(2017/07/24)
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- Ultrafast dynamics in aromatic cation based ionic liquids: A femtosecond raman-induced kerr effect spectroscopic study
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We studied the ultrafast dynamics of 40 aromatic cation based ionic liquids (ILs) by means of femtosecond Ramaninduced Kerr effect spectroscopy. The low-frequency Kerr spectra (ca. 0.3700 cm1) of the ILs were obtained from the Kerr transients by Fourier-Transform deconvolution analysis. The low-frequency Kerr spectra in the frequency range less than 200 cm-1 coming mainly from the intermolecular vibrations for the ILs were discussed in terms of (i) anion dependence, (ii) imidazolium cations vs. pyridinium cations, (iii) alkyl group dependence, and (iv) effect of methylation in aromatic cations. Several liquid properties, such as density, viscosity, electrical conductivity, and surface tension, of the present sample ILs at 293K were also estimated in this study. We clarified that the aromatic cation based ILs show a different relation of the first moment of the low-frequency spectral band to the bulk liquid parameter, which is the square root of surface tension divided by liquid density, from aprotic molecular liquids. The slope of the first moment to the bulk parameter for the aromatic cation based ILs is gentler than that for aprotic molecular liquids.
- Shirota, Hideaki,Kakinuma, Shohei,Takahashi, Kotaro,Tago, Akito,Jeong, Hocheon,Fujisawa, Tomotsumi
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supporting information
p. 1106 - 1128
(2016/10/11)
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- Bronsted acids in ionic liquids: How acidity depends on the liquid structure
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Gutmann Acceptor Number (AN) values have been determined for Bronsted acid-ionic liquid mixtures, over a wide compositional range. Four systems of general formula [C2mim][A]-HA (A- = bistriflamide, [NTf2]-; triflate, [OTf]-; mesylate, [OMs]-; or acetate, [OAc]-, [C2mim]+ = 1-ethyl-3-methylimidazolium cation) were studied. A library of Bronsted acidic systems of varying acidity was constructed and the AN parameter was found to be a convenient approach for quantifying their acidity. HOAc, HOMs and HOTf, when dissolved in ionic liquids, were found to associate with the respective anions to form hydrogen-bonded anionic clusters, [A(HA)x]-. In contrast, HNTf2 was solubilised as a discrete, undissociated molecule. AN values were sensitive to the presence of anionic clusters; acidity could be buffered to a particular AN by binding the solubilised acid in the anionic cluster form. Overall, a simple way to manipulate and quantify the Bronsted acidity of acid-ionic liquid mixtures was demonstrated, and measured AN values were related to liquid speciation. This journal is
- McCune, Jade A.,He, Peizhao,Petkovic, Marina,Coleman, Fergal,Estager, Julien,Holbrey, John D.,Seddon, Kenneth R.,Swadba-Kwasny, Malgorzata
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p. 23233 - 23243
(2015/01/08)
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- On the solubility of wood in non-derivatising ionic liquids
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Norway spruce wood was mechanically pulverized to varying degrees. The solubility of the wood samples, in a range of common ionic and molecular solvents, was quantified using a novel 31P NMR technique. The results show that intact wood is not soluble under mild treatment conditions, in cellulose-dissolving or swelling solvents.
- Kylloenen, Lasse,Parviainen, Arno,Deb, Somdatta,Lawoko, Martin,Gorlov, Mikhail,Kilpelaeinen, Ilkka,King, Alistair W. T.
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supporting information
p. 2374 - 2378
(2013/09/12)
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- Monitoring of liquid-phase organic reactions by photoelectron spectroscopy
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There are strings attached: After linking the reacting groups to head groups of ionic liquids to drastically lower the vapour pressures of the reactants, ordinary liquid-phase organic reactions can be monitored by in situ X-ray photoelectron spectroscopy. This approach is demonstrated for the nucleophilic substitution of an alkyl amine and an alkyl chloride moiety, which are attached to the cation and anion of ionic liquids, respectively. Copyright
- Kolbeck, Claudia,Niedermaier, Inga,Taccardi, Nicola,Schulz, Peter S.,Maier, Florian,Wasserscheid, Peter,Steinrueck, Hans-Peter
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scheme or table
p. 2610 - 2613
(2012/04/17)
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- A convenient synthesis of triflate anion ionic liquids and their properties
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A solvent- and halogen-free synthesis of high purity triflate ionic liquids via direct alkylation of organic bases (amines, phosphines or heterocyclic compounds) with methyl and ethyl trifluoromethanesulfonate (methyl and ethyl triflate) has been developed. Cheap and non-toxic dimethyl and diethyl carbonate serve as source for the methyl and ethyl groups in the preparation of methyl and ethyl triflate by this invented process. The properties of ionic liquids containing the triflate anion are determined and discussed.
- Ignat'ev, Nikolai V.,Barthen, Peter,Kucheryna, Andryi,Willner, Helge,Sartori, Peter
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experimental part
p. 5319 - 5338
(2012/08/28)
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- Arylation of sensitive 1-(Pyrrolidin-1-yl)-diazen-1-ium-diolate in ionic liquids
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The purpose of this research was to investigate the stability and reactivity of 1-(pyrrolidin-1-yl)diazen-1-ium-1,2-diolate (PYRRO/NO) in dimethylformamide (DMF, as the reference solvent) and compare them to those obtained using different ionic liquids. The results of our experiments showed that PYRRO/NO is more stable (based on reactivity) in ionic liquid [EMIM][Ms] (with reaction yields up to 52%) than in DMF, that substitution products can be separated directly and quantitatively from the ionic liquid using a single flash-column separation, and that the ionic liquids can also be recovered and reused in a second iteration of the same reaction to achieve similar yields.
- Velazquez, Carlos A.,Lynn, Geoffrey M.,Kumar, Vineet,Keefer, Larry K.,Malhotra, Sanjay V.
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experimental part
p. 1322 - 1332
(2010/07/04)
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- Efficient intramolecular hydroalkoxylation/cyclization of unactivated alkenols mediated by lanthanide triflate ionic liquids
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Lanthanide triflates, Ln(OTf)3, serve as efficient catalysts for the intramolecular hydroalkoxylation (HO)/cyclization of primary/secondary and aliphatic/aromatic hydroxyalkenes in room temperature ionic liquids (RTlLs). Cyclizations are effective in the formation of five-and sixmembered oxygen heterocycles with Markovnikov-type selectivity. Reaction rates exhibit first-order dependence on [Ln3+] and [substrate].
- Dzudza, Alma,Marks, Tobin J.
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supporting information; experimental part
p. 1523 - 1526
(2009/09/06)
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- METHOD FOR PRODUCING ONIUM SALTS COMPRISING ALKYL ANIONS OR ARYL SULFONATE ANIONS OR ALKYL ANIONS OR ARYL CARBOXYLATE ANIONS HAVING A LOW HALIDE CONTENT
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The invention relates to a method for producing onium salts comprising alkyl anions or aryl sulfonate anions or alkyl carboxylate anions or acryl carboxylate anions by reacting an onium halide with an alkyl silyl ester or trialkyl silyl ester of an alkyl sulfonic acid or aryl sulfonic acid or an alkyl carboxylic acid or aryl carboxylic acid or the anhydrides thereof.
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Page/Page column 29
(2008/06/13)
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- A PURIFICATION METHOD OF IONIC LIQUIDS TO OBTAIN THEIR HIGH PURITY
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Disclosed is an ionic liquid purification method for preparing high purity ionic liquids which can be used as solvents for organic, inorganic and biochemical reactions or as electrolytic solutions of storage batteries, secondary batteries, or fuel batteries, by removing organic halide salts, organic salts, halide residues, acid residues, excess alkali metals and so on, from unpurified ionic liquids using liquid/liquid continuous extraction.
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- Antistatic composition
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An antistatic composition comprises (a) at least one ionic salt consisting of a nonpolymeric nitrogen onium cation and a weakly coordinating fluoroorganic anion, the conjugate acid of the anion being a superacid; and (b) at least one thermoplastic polymer. The composition exhibits good antistatic performance over a wide range of humidity levels.
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