- Improved solubilization of pyromellitic dianhydride and 4,4′-oxydianiline in ionic liquid by the addition of zwitterion and their polycondensation
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Three different ionic liquids were prepared and examined as solvents for polyimide synthesis. The solubility of 4,4′-oxydianiline and pyromellitic dianhydride as starting materials in ionic liquids was first evaluated, and then their polycondensation was carried out. Although these starting materials were hardly soluble in 1-benzyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide (3), addition of imidazolium type zwitterion, 1-(1-butyl-3-imidazolio)butane-4-sulfonate (ZI), certainly improved their solubility. When 3 containing 40 mol % ZI was used, nothing was phase separated from this mixed solution containing both starting materials after cooling down to room temperature. After preparing prepolymer in 3 containing 40 mol % of ZI at room temperature, polycondensation was carried out in the same solution at 100, 200, and then 300 °C for every 1 h to obtain polyimide. An inherent viscosity of the obtained polyimide (0.05 g in 10 ml concentrated sulfuric acid) was 1.3 dL g-1, higher than that prepared in only 3 (0.9 dL g-1). The higher average molecular weight of the polyimide was attributed to the improved solubility of the starting materials by the addition of ZI that enabled the preparation of the prepolymer, poly(amide acid), without heating before imidation.
- Tamada, Masahiro,Hayashi, Takahiro,Ohno, Hiroyuki
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- Ion gels prepared by in situ radical polymerization of vinyl monomers in an ionic liquid and their characterization as polymer electrolytes
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To realize polymer electrolytes with high ionic conductivity, we exploited the high ionic conductivity of an ionic liquid. In situ free radical polymerization of compatible vinyl monomers in a room temperature ionic liquid, 1-ethyl-3-methyl imidazolium bis(trifluoromethane sulfonyl)imide (EMITFSI), afforded a novel series of polymer electrolytes. Polymer gels obtained by the polymerization of methyl methacrylate (MMA) in EMITFSI in the presence of a small amount of a cross-linker gave self-standing, flexible, and transparent films. The glass transition temperatures of the gels, which we named ion gels , decreased with increasing mole fraction of EMITFSI and behaved as a completely compatible binary system of poly(methyl methacrylate) (PMMA) and EMITFSI. The temperature dependence of the ionic conductivity of the ion gels followed the Vogel-Tamman-Fulcher (VTF) equation, and the ionic conductivity at ambient temperature reached a value close to 10-2 S cm-1. Similarly to the behavior of the ionic liquid, the cation in the ion gels diffused faster than the anion. The number of carrier ions, calculated from the Nernst-Einstein equation, was found to increase for an ion gel from the corresponding value for the ionic liquid itself. The cation transference number increased with decreasing EMITFSI concentration due to interaction between the PMMA matrix and the TFSI- anion, which prohibited the formation of ion clusters or associates, as was the case for the ionic liquid itself.
- Susan, Md. Abu Bin Hasan,Kaneko, Taketo,Noda, Akihiro,Watanabe, Masayoshi
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- Novel viologen derivatives for electrochromic ion gels showing a green-colored state with improved stability
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We successfully synthesized a novel viologen derivative (1,1′-bis(3-fluoro-4-(trifluoromethyl)phenyl)-4,4′-bipyridinium bis(trifluoromethylsulfonyl)imide, TFMFPhV(TFSI)2) exhibiting a green-colored state. We selected cyanophenyl viologen (CNPhV2+), a conventional electrochromic (EC) chromophore with a green color indication, to compare EC performance. Ion gels consisting of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMI][TFSI]) were employed as a solid-state electrolyte for EC devices (ECDs). In comparison to CNPhV2+-containing devices, the ECDs with TFMFPhV2+ showed higher transmittance contrast, larger coloration efficiency, faster coloration and bleaching responses, and better coloration/bleaching operational stability. Cyclic voltammetry revealed that the more stable redox behavior of TFMFPhV2+ is the origin of the outstanding ECD performance.
- Oh, Hwan,Seo, Dong Gyu,Yun, Tae Yong,Lee, Seong Been,Moon, Hong Chul
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- NH3absorption in Br?nsted acidic imidazolium- And ammonium-based ionic liquids
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This paper reports the NH3 solubilities and absorption mechanisms in the imidazolium- and ammonium-based ionic liquids. The cations were 1-methyl-3-(4-sulfobutyl)-imidazolium, 1-(2-hydroxyethyl)-3-methylimidazolium, 1-ethyl-3-methyl-imidazolium, N-carboxymethyl-N,N,N-trimethylammonium, N-(2-hydroxyethyl)-N,N,N-trimethylammonium, and N-butyl-N,N,N-trimethylammonium, whereas the anions were bis(trifluoromethanelsulfonyl)amide, tris(pentafluoroethyl)trifluorophosphate, trifluoromethylsulfonate, and hydrogensulfate. The Br?nsted acidic ionic liquids, consisting of sulfo and carboxy groups and hydrogensulfate anion, absorbed larger amounts of NH3, followed by the hydroxy-functionalized and nonfunctionalized ionic liquids. The NMR and Raman spectra indicated that the Br?nsted acidic ionic liquids absorbed NH3 as both the molecular ammonia (physical absorption) and the ammonium cation (chemical absorption). Although the hydroxy group strongly interacted with NH3, the hydroxy-functionalized ionic liquids dissolved NH3 only physically, similar to the nonfunctionalized ionic liquids. In conclusion, the chemical absorption brought about the higher NH3 solubilities in the Br?nsted acidic imidazolium- and ammonium-based ionic liquids. This journal is
- Makino, Takashi,Kanakubo, Mitsuhiro
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- Structural diversity in hybrid vanadium(iv) oxyfluorides based on a common building block
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There are only limited reports on vanadium(iv) oxyfluorides (VOFs) with extended crystal structures. Here we expand and enrich the list of existing VOFs with a series of 14 new materials "VOF-n (n = 1-14)" prepared using ionothermal and solvothermal synthesis methods. All of these materials arise from the condensation of a dimeric structural motif. These VOFs can be classified into three groups depending on their key structural features; layer structures: VOF-1 "[HN2C7H6][V 2O2F5]", VOF-2 "[HN2C 4H4][V2O2F5]", VOF-3 "[HN2C3H4][V2O 2F5]" and VOF-4 "V2(N 2C4H4)O2F4", ladder like structures: VOF-5 "[NH4(HN2C3H 4)][V2O2F6]", VOF-6 "[K(HN2C3H4)][V2O 2F6]", VOF-7 "[HNH2CH 2CH3][VOF3]", VOF-8 "[HN 2C7H6][VOF3]", VOF-9 "[H2N2C4H6][V2O 2F6]", VOF-10 "β-RbVOF3", VOF-11"α-KVOF3", VOF-12 "β-KVOF 3", VOF-13 "[H2(NH2) 2(CH2)2][V2O2F 6]", and a chain structure: VOF-14 "[H2N 2C6H12][V2O2F 7]". The crystal structures of VOF-n are presented, and their synthetic and structural relationships are discussed.
- Aidoudi, Farida H.,Black, Cameron,Arachchige, Kasun S. Athukorala,Slawin, Alexandra M. Z.,Morris, Russell E.,Lightfoot, Philip
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- Electrochemical fluorination (Simons process) - A powerful tool for the preparation of new conducting salts, ionic liquids and strong Br?nsted acids
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Electrochemical fluorination (Simons process) provides a cheap commercial access to a series of tris(perfluoroalkyl)diflurophosphoranes. These substances are convenient starting material for the preparation of various fluoro-chemicals. The synthesis of ne
- Ignat'ev,Willner,Sartori
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- Coordination and extraction of mercury(ii) with an ionic liquid-based thione extractant
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A neutral thione extractant, 1,3-diethylimidazole-2-thione (C 2C2ImT), was prepared from an ionic liquid (IL), 1,3-diethylimidazolium acetate, and used within a hydrophobic ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethane)sulfonamide ([C 2mim][NTf2]), to extract Hg(ii) from aqueous solutions of HgCl2 or Hg(OAc)2. Investigations of the extraction mechanism, spectroscopic analyses of the extracted species, and crystallographic studies of the interactions of C2C2ImT with Hg(ii) are reported, including the first structurally characterized Hg-NTf2 coordination compound, Hg(C2C2ImT)2(NTf 2)2. Coordination complexes of the thione ligand with Hg(ii) show variability in coordination numbers and geometries with stoichiometry, suggesting that the extraction mechanism is dependent on the speciation of mercury in aqueous solution. HgCl2 can form neutral, extractable complexes with the thione in aqueous solution. Hg(OAc)2 dissociates on dissolution in water and Hg(ii) is extracted through a cation exchange mechanism involving [Hg(C2C2ImT) 2]2+ ions. The precipitation of neutral mercury complexes from the IL following the extraction of excess mercury suggests a simple and unusual way to recycle the IL.
- Lu, Wenjuan,Barber, Patrick S.,Kelley, Steven P.,Rogers, Robin D.
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- Investigation on physical and electrochemical properties of three imidazolium based ionic liquids (1-hexyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide and 1-butyl-3-methylimidazolium methylsulfate)
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Three types of imidazolium based ionic liquids, 1-hexyl-3-methylimidazolium tetrafluoroborate ([HMIM][BF4]), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([EMIM][NTf2]) and 1-butyl-3-methylimidazolium methylsulfate ([BMIM][MeSO4]) were prepared and a variety of their fundamental properties such as kinematic (ν) and dynamic (η) viscosities, thermal stability, surface tension (σ), refractive index (nD), pH and density (ρ) were investigated as a function of temperature. The coefficients of thermal expansion (αp) of the pure liquids were also calculated from the experimental values of the density at different temperatures. Electrochemical studies of these pure fluids as media were also studied at screen printed glassy carbon electrode (SP-GCE). The measurements were performed on a single drop of ionic liquids at surface of a screen-printed three electrode cell. The results showed an ideal wide range of potential windows for studies of electrochemical behavior of some species such as hydrogen sulfide and thiols in the lipophilic and hydrophilic ionic liquids. These properties were studied for special purposes such as development of electroanalytical methods for trace determination of organosulfur compounds in petroleum and its products.
- Miran Beigi, Ali Akbar,Abdouss, Majid,Yousefi, Maryam,Pourmortazavi, Seied Mahdi,Vahid, Amir
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- Ionic liquids based on (fluorosulfonyl)(pentafluoroethanesulfonyl)imide with various oniums
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New hydrophobic ionic liquids based on (fluorosulfonyl) (pentafluoroethanesulfonyl)imide ([(FSO2)(C2F 5SO2)N]-, FPFSI-) anion with various oniums, including imidazolium, tetraalkyl ammonium, pyrrolidinium, and piperidinium, were prepared and characterized. Their physicochemical and electrochemical properties, including phase transitions, thermal stability, viscosity, density, specific conductivity and electrochemical windows, were extensively characterized, and were comparatively studied with the corresponding ionic liquids containing the isomeric but symmetric TFSI- ([(CF 3SO2)2N]-) anion. These new FPFSI--based ionic liquids display low melting points, low viscosities, good thermal stability, and wide electrochemical windows allowing Li deposition/dissolution. All these desired properties suggest they are potential electrolyte materials for Li (or Li-ion) batteries.
- Liu, Kai,Zhou, Yi-Xuan,Han, Hong-Bo,Zhou, Si-Si,Feng, Wen-Fang,Nie, Jin,Li, Hong,Huang, Xue-Jie,Armand, Michel,Zhou, Zhi-Bin
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- ZIF-8-porous ionic liquids for the extraction of 2,2,3,3-tetrafluoro-1-propanol and water mixture
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The design of stable ionic liquids (ILs) has become crucial for efficient liquid-liquid extraction (LLE) of alcohol and water. Porous ionic liquids (PILs), as a special class of ILs, have attracted attention by virtue of their unique porous structure and IL characteristics. In this research, a series of zeolitic imidazolate framework-8 based porous ionic liquids (ZIF-8-PILs) were synthesized by simply mixing a solution of zeolitic imidazolate framework-8 (ZIF-8) and rationally designed ILs. The introduction of ZIF-8 resulted in a unique liquid porous structure and molecular sieve for ZIF-8-PILs. The improved extraction properties endowed ZIF-8/[Bpy][NTf2] with more efficiency for the separation of 2,2,3,3-tetrafluoro-1-propanol (TFP) and water with 88.1% TFP extraction rate and steady reuse. The excellent extraction performance of ZIF-8-PILs is discussed in relation to their textural property and unique intermolecular interaction.
- Wang, Zenghui,Zhao, Pingping,Wu, Jimin,Gao, Jun,Zhang, Lianzheng,Xu, Dongmei
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- Coordination of terpyridine to Li+ in two different ionic liquids
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On the basis of 7Li NMR experiments, the complex-formation reaction between Li+ and the tridentate N-donor ligand terpyridine was studied in the ionic liquids [emim][NTf2] and [emim][ClO 4] as solvents. For both ionic liquids, the NMR data implicate the formation of [Li(terpy)2]+. Density functional theory calculations show that partial coordination of terpyridine involving the coordination of a solvent anion can be excluded. In contrast to the studies in solution, X-ray diffraction measurements led to completely different results. In the case of [emim][NTf2], the polymeric lithium species [Li(terpy)(NTf2)]n was found to control the stacking of this complex, whereas crystals grown from [emim][ClO4] exhibit the discrete dimeric species [Li(terpy)(ClO4)]2. However, both structures indicate that each lithium ion is formally coordinated by one terpy molecule and one solvent anion in the solid state, suggesting that charge neutralization and π stacking mainly control the crystallization process.
- Pokorny, Klaus,Schmeisser, Matthias,Hampel, Frank,Zahl, Achim,Puchta, Ralph,Van Eldik, Rudi
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- Liquid Electrolytes Based on Ionic Liquids for Lithium-Ion Batteries
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Low-melting temperature ionic liquids (ILs), based on aliphatic quaternary ammonium N1xxx and 1-ethyl-3-methylimidazolium cations with the imide anion, were prepared and characterized. The physicochemical and electrochemical properties of these
- Le, My Loan Phung,Tran, Ngoc Anh,Ngo, Hoang Phuong Khanh,Nguyen, Truong Giang,Tran, Van Man
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- Solvent extraction of Sr2+ and Cs+ based on room-temperature ionic liquids containing monoaza-substituted crown ethers
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A series of N-alkyl aza-18-crown-6 ethers were synthesized and characterized by NMR spectroscopy and mass spectrometry. These monoaza-substituted crown ethers in ionic liquids were investigated as recyclable extractants for separation of Sr2+ and Cs+ from aqueous solutions. The pH-sensitive complexation capability of these ligands allows for a facile stripping process to be developed so that both macrocyclic ligands and ionic liquids can be reused. The extraction efficiencies and selectivities of these monoaza-substituted crown ethers for Na+, K+, Cs+, and Sr2+ were studied in comparison to those of dicyclohexano-18-crown-6 under the same conditions. The extraction selectivity order for dicyclohexano-18-crown-6 in the ionic liquids investigated here was K+ ? Sr2+ > Cs + > Na+. The extraction selectivity order for N-alkyl aza-18-crown-6, in which the alkyl group is varied systematically from ethyl to n-dodecyl, was Sr2+ ? K+ > Cs+ > Na+ in 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]amide and 1-butyl-3-methylimidazolium bis[(trifiuoromethyl)suffonyl]amide and K+ > Sr2+ > Cs+ > Na+ in 1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl] amide and 1-octyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]amide. The strong dependence of selectivity on the type of ionic liquid indicates an important role played by solvation in solvent extraction processes based on ionic liquids. The optimization of macrocyclic ligands and ionic liquids led to an extraction system that is highly selective toward Sr2+.
- Luo, Huimin,Dai, Sheng,Bonnesen, Peter V.
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- Lower critical solution temperature phase behavior of poly(n -butyl methacrylate) in ionic liquid mixtures
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Ionic liquids feature a combination of properties that make them very interesting solvents for polymers, but many questions remain regarding the thermodynamics of polymer/ionic liquid solutions. In this work, the lower-critical-solution-temperature (LCST) phase behavior of poly(n-butyl methacrylate) (PnBMA) in mixtures of the ionic liquids 1-butyl-3- methylimidazolium:bis(trifluoromethylsulfonyl)imide ([BMIm][TFSI]) and 1-ethyl-3-methylimidazolium:TFSI ([EMIm][TFSI]) is characterized by transmittance, light scattering, and small-angle neutron scattering measurements. Several relevant thermodynamic parameters are easily tuned by varying the ionic liquid composition. In particular, the cloud point, spinodal, and Θ temperatures are all found to increase linearly with [BMIm] content. The interaction parameters, χ, are determined as a function of temperature and concentration using three different methods, and the results from each method are compared. The entropic and enthalpic components of the interaction parameter, χ, are also found to vary linearly with [BMIm] content in the ionic liquid, increasing and decreasing, respectively. The increase in the enthalpic driving force for mixing with increasing [BMIm] content dominates over the decrease in the entropic penalty for mixing, leading to improved solubility. This result is discussed in terms of molecular interactions and oriented solvation. This work characterizes the solution thermodynamics of one representative system in a very interesting class of polymer solutions, and provides insight into the molecular mechanisms underlying its LCST phase behavior.
- Hoarfrost, Megan L.,He, Yanpu,Lodge, Timothy P.
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- Directed Phase Transfer of an FeII4L4 Cage and Encapsulated Cargo
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Supramolecular capsules can now be prepared with a wide range of volumes and geometries. Consequently, many of these capsules encapsulate guests selectively by size and shape, an important design feature for separations. To successfully address practical separations problems, however, a guest cannot simply be isolated from its environment; the molecular cargo must be removed to a separate physical space. Here we demonstrate that an FeII4L4 coordination cage 1 can transport a cargo spontaneously and quantitatively from water across a phase boundary and into an ionic liquid layer. This process is triggered by an anion exchange from 1[SO4] to 1[BF4]. Upon undergoing a second anion exchange, from 1[BF4] to 1[SO4], the cage, together with its encapsulated guest, can then be manipulated back into a water layer. Furthermore, we demonstrate the selective phase transfer of cationic cages to separate a mixture of two cages and their respective cargoes. We envisage that supramolecular technologies based upon these concepts could ultimately be employed to carry out separations of industrially relevant compounds.
- Grommet, Angela B.,Nitschke, Jonathan R.
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- Densities and viscosities of the binary mixtures of 1-ethyl-3- methylimidazolium bis(trifluoromethylsulfonyl)imide with N -methyl-2-pyrrolidone or ethanol at T = (293.15 to 323.15) K
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Figure Persented: The densities and viscosities of 1-ethyl-3- methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf2]) + N-methyl-2-pyrrolidone (NMP) and [EMIM][NTf2] + ethanol mixtures were investigated over the mole fraction range from (0.1 to 0.9) and at temperatures from (293.15 to 323.15) K at intervals of 5 K. The densities can be well-represented by the quadratic equation, and the viscosities can be represented in the form of the Vogel equation. The excess molar volumes (V E) and viscosity deviations (Δη) were calculated, and the results were fitted to the Redlich-Kister equation using a multiparametric nonlinear regression method. The estimated parameters of the Redlich-Kister equation and standard deviation were also presented. The results showed that the densities and viscosities were dependent strongly on NMP or ethanol content. Comparatively, the viscosity deviation Δ η was more sensitive to temperature than the excess molar volume VE.
- Yao, Hongwei,Zhang, Shuheng,Wang, Jieli,Zhou, Qing,Dong, Haifeng,Zhang, Xiangping
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- Distillable ionic liquids: Reversible amide OAlkylation
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Put it in reverse: The recycling of ionic liquids (ILs) by distillation of the regenerated volatile precursors was demonstrated to be feasible by using low-cost amide-cation-derived aprotic ionic liquids prepared from reversible Oalkylation. The low visco
- Chen, Zheng-Jian,Xi, Hong-Wei,Lim, Kok Hwa,Lee, Jong-Min
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- A Triphasic Sorting System: Coordination Cages in Ionic Liquids
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Host-guest chemistry is usually carried out in either water or organic solvents. To investigate the utility of alternative solvents, three different coordination cages were dissolved in neat ionic liquids. By using 19F NMR spectroscopy to monitor the presence of free and bound guest molecules, all three cages were demonstrated to be stable and capable of encapsulating guests in ionic solution. Different cages were found to preferentially dissolve in different phases, allowing for the design of a triphasic sorting system. Within this system, three coordination cages, namely Fe4L6 2, Fe8L12 3, and Fe4L4 4, each segregated into a distinct layer. Upon the addition of a mixture of three different guests, each cage (in each separate layer) selectively bound its preferred guest.
- Grommet, Angela B.,Bolliger, Jeanne L.,Browne, Colm,Nitschke, Jonathan R.
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- Acute toxicity of cu-mof nanoparticles (Nanohkust-1) towards embryos and adult zebrafish
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Metal-organic frameworks (MOFs) demonstrate unique properties, which are prospective for drug delivery, catalysis, and gas separation, but their biomedical applications might be limited due to their obscure interactions with the environment and humans. It is important to understand their toxic effect on nature before their wide practical application. In this study, HKUST-1 nanoparticles (Cu-nanoMOF, Cu3 (btc)2, btc = benzene-1,3,5-tricarboxylate) were synthesized by the microwave (MW)-assisted ionothermal method and characterized by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM) techniques. The embryotoxicity and acute toxicity of HKUST-1 towards embryos and adult zebrafish were investigated. To gain a better understanding of the effects of Cu-MOF particles towards Danio rerio (D. rerio) embryos were exposed to HKUST-1 nanoparticles (NPs) and Cu2+ ions (CuSO4 ). Cu2+ ions showed a higher toxic effect towards fish compared with Cu-MOF NPs for D. rerio. Both forms of fish were sensitive to the presence of HKUST-1 NPs. Estimated LC50 values were 2.132 mg/L and 1.500 mg/L for zebrafish embryos and adults, respectively. During 96 h of exposure, the release of copper ions in a stock solution and accumulation of copper after 96 h were measured in the internal organs of adult fishes. Uptake examination of the major internal organs did not show any concentration dependency. An increase in the number of copper ions in the test medium was found on the first day of exposure. Toxicity was largely restricted to copper release from HKUST-1 nanomaterials structure into solution.
- Abramenko, Natalia,Deyko, Gregory,Abkhalimov, Evgeny,Isaeva, Vera,Pelgunova, Lyubov,Krysanov, Eugeny,Kustov, Leonid
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- Various metal nanoparticles produced by accelerated electron beam irradiation of room-temperature ionic liquid
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Various metal nanoparticles including base metal were produced by a brief accelerated electron beam irradiation of 1-alkyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)amide room-temperature ionic liquid without a stabilizing agent, which is usually employed so as to prevent aggregation.
- Tsuda, Tetsuya,Sakamoto, Taiki,Nishimura, Yoshitomo,Seino, Satoshi,Imanishi, Akihito,Kuwabata, Susumu
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- Excess Molar Volume and Viscosity Deviation of [C2mim][NTf2]/[C4mim][NTf2] + DMC/DEC
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Two hydrophobic ionic liquids (ILs) 1-alkyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C2mim][NTf2] and [C4mim][NTf2]) were synthesized. The binary mixtures of the two ILs were prepared with dimethyl carbonate (DMC) or diethyl carbonate (DEC) over the entire mole fraction range, respectively. The density and viscosity of the binary mixtures were determined by an automated DMA 5000 M and a Lovis 2000 ME Anton Paar Rotational Stabinger Viscometer at temperatures ranging from 288.15 to 328.15 K. The uncertainties of the density and viscosity are ur(δ) = 0.00120 and ur(δ) = 0.01. The excess molar volumes and viscosity deviations were calculated for the four binary mixtures by the measurement values. The effects of the extension of the alkyl chain of the cation and anion on the above properties are discussed. The effects of the methyl introduction on the cation was also discussed with the literature. The excess molar volumes and viscosity deviations were fitted versus mole fraction according to the Redlich-Kister equation. The thermal expansion coefficients of the systems were calculated according to the density values.
- Liu, Qingshan,Zhao, Liwei,Zheng, Qige,Mou, Lin,Zhang, Pengfei
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- Ultrafast Ligand Self-Exchanging Gadolinium Complexes in Ionic Liquids for NMR Field Probes
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Concurrent magnetic field monitoring in MRI with an array of NMR field probes allows for reducing image imperfections. High 19F concentrations together with short relaxation times are basic probe properties. We present the NMR properties of [Gd
- Looser, Anna,Barmet, Christoph,Fox, Thomas,Blacque, Olivier,Gross, Simon,Nussbaum, Jennifer,Pruessmann, Klaas P.,Alberto, Roger
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- The effect of light penetration depth on the LCST phase behavior of a thermo- and photoresponsive statistical copolymer in an ionic liquid
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A reflection cloud point technique allows for rapid screening of light-dependent phase separation temperatures of thermo- and photoresponsive polymer/ionic liquid solutions as a function of sample thickness, molecular weight, and copolymer composition. We systematically investigate the lower critical solution temperature (LCST) phase behavior of poly(benzyl methacrylate-stat-(4-phenylazophenyl methacrylate)). Under UV light, the photoresponsive azobenzene-based repeat unit becomes more polar as the cis form dominates, increasing its solubility in the ionic liquids 1-ethyl-3-methyl imidazolium and 1-butyl-3-methyl imidazolium bis(trifluoromethanesulfonyl)imide. This light-dependent polarity change leads to two phase separation temperatures, depending on the illumination wavelength. Under visible light, which drives the azobenzene moiety into the trans ground state, the LCST shows no sample thickness dependence. Under UV light, however, sample thickness plays a significant role. Samples of around 1 mm thickness show no apparent difference under UV and visible light, whereas thinner samples show an increasing difference between the phase separation temperatures with decreasing sample thickness. Neither phase separation temperature exhibits a significant dependence on molecular weight. Increasing the photoresponsive monomer content did not lead to an increase in the difference between the phase separation temperatures at fixed thickness, due to a concomitant increase in UV light absorbed at the sample surface.
- Hall, Cecilia C.,Rivera, Cecelia A.,Lodge, Timothy P.
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- Halogen bonding effect on electrochemical anion oxidation in ionic liquids
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Three Ionic liquids (ILs) based on an imidazolium core have been compared and used as solvents for the oxidation of various anions. Electrochemical experiments as well as NMR titrations and X-ray diffraction analyses unambiguously confirm the crucial role of non-covalent halogen bonding on the oxidation potentials and consequently the electrochemical window of the respective ILs.
- Alvarez, Marie Stacey,Fave, Claire,Groni, Sihem,Houzé, Cedric,Sch?llhorn, Bernd
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supporting information
p. 7587 - 7593
(2021/09/22)
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- Preparation method of dialkylimidazole bis(trifluoromethylsulfonyl)imide salt
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The invention discloses a preparation method of a dialkylimidazole bis(trifluoromethylsulfonyl)imide salt. The method comprises the following steps: 1, reacting alkylimidazole with sulfate in an organic solvent, and layering the obtained solution to obtain a crude dialkylimidazole sulfate product; 2, washing the crude dialkylimidazole sulfate product, carrying out reduced pressure distillation, and drying the obtained product to obtain dialkylimidazole sulfate; 3, reacting the dialkylimidazole sulfate with a bis(trifluoromethylsulfonyl)imide metal salt, and layering the obtained solution to obtain a crude dialkylimidazole bis(trifluoromethylsulfonyl)imide salt product; and 4, washing the crude dialkylimidazole bis(trifluoromethylsulfonyl)imide salt product, carrying out reduced pressure distillation, and drying the obtained product to obtain the target product dialkylimidazole bis(trifluoromethylsulfonyl)imide salt. The method has the advantages of mild reaction conditions, simple operation steps, realization of high yield, high purity and low halogen ion content of the prepared product, and suitableness for promotion and application.
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- Nanoreactors stable up to 200 °c: A class of high temperature microemulsions composed solely of ionic liquids
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It is a challenge to develop microemulsions which can serve as nanoreactors for the synthesis of nanoparticles and chemical reactions at high temperature. In this work, a class of novel high temperature microemulsions consisting solely of ionic liquids have been designed and prepared for the first time. It is found that nanoscale droplets formed in the ionic liquid microemulsions can be maintained up to 200 °C, and the size distribution of the droplets can be easily tuned by selection of the ionic liquids and varying compositions of the systems. By using such microemulsions as nanoreactors, porous metals such as Pt have been prepared at 180 °C without using any purposely added reductant.
- Pei, Yuanchao,Ru, Jie,Yao, Kaisheng,Hao, Lihui,Li, Zhiyong,Wang, Huiyong,Zhu, Xingqi,Wang, Jianji
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supporting information
p. 6260 - 6263
(2018/06/22)
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- Dissolution of oligo(tetrafluoroethylene) and preparation of poly(tetrafluoroethylene)-based composites by using fluorinated ionic liquids
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Fluorophilic ionic liquids (ILs) showing enhanced compatibility with poly(tetrafluoroethylene) (PTFE) have been newly synthesised. The as-designed ILs contributed both to the dissolution of PTFE oligomers and to the preparation of composites with PTFE with no fear of bleed-out of the ILs.
- Tsurumaki, Akiko,Ohno, Hiroyuki
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supporting information
p. 409 - 412
(2018/02/27)
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- Evidence for the spontaneous formation of N-heterocyclic carbenes in imidazolium based ionic liquids
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We present a study of the reactions of aldehydes in ionic liquids which gives evidence for the spontaneous formation of N-heterocyclic carbenes in ionic liquids based on 1,3-dialkyl substituted imidazolium cations from the lack of a deuterium isotope effect on the reaction of these ionic liquids with aldehydes.
- Daud,Bakis,Hallett,Weber,Welton
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supporting information
p. 11154 - 11156
(2017/10/17)
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- Tandem dissolution of UO3 in amide-based acidic ionic liquid and: In situ electrodeposition of UO2 with regeneration of the ionic liquid: A closed cycle
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A closed cycle is demonstrated for the tandem dissolution and electroreduction of UO3 to UO2 with regeneration of the acidic ionic liquid. The dissolution is achieved by use of the acidic ionic liquid [DMAH][NTf2] in [EMIM][NTf2] serving as the diluent. A sequential dissolution, electroreduction, and regeneration cycle is presented.
- Wanigasekara, Eranda,Freiderich, John W.,Sun, Xiao-Guang,Meisner, Roberta A.,Luo, Huimin,Delmau, L?titia H.,Dai, Sheng,Moyer, Bruce A.
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supporting information
p. 10151 - 10154
(2016/07/11)
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- Preparation method and application of ionic liquid
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The invention relates to a preparation method of ionic liquid. The preparation method comprises the following steps: dissolving a water-soluble compound of which negative ions are trifluoro-alkyl sulfimide ions in water to prepare a first aqueous solution; dissolving a water-soluble compound of which positive ions are quaternary ammonium ions or imidazole ions in water to prepare a second aqueous solution; mixing the first aqueous solution and the second aqueous solution together according to a mole ratio of the negative ions to the positive ions of 1:(0.9-1.1), and then performing separation to obtain a crude product; rinsing the crude product to obtain a high-purity product; and performing vacuum drying on the high-purity product to obtain the ionic liquid. The preparation scheme of the ionic liquid provided by the invention is simple and feasible, and is conducive to industrialization; the prepared ionic liquid is high in purity, low in water content, and low in foreign ion content; and the ionic liquid of this type is high in thermal decomposition temperature and low in chroma, and can be used as an antistatic agent with high optical transparence requirements for high-temperature molding plastics.
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Paragraph 0029; 0030; 0031; 0032; 0033; 0034
(2017/01/12)
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- Ionic fluids containing both strongly and weakly interacting ions of the same charge have unique ionic and chemical environments as a function of ion concentration
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Liquid multi-ion systems made by combining two or more salts can exhibit charge ordering and interactions not found in the parent salts, leading to new sets of properties. This is investigated herein by examining a liquid comprised of a single cation, 1-ethyl-3-methylimidazolium ([C2mim]+), and two anions with different properties, acetate ([OAc]-) and bis(trifluoromethylsulfonyl)imide ([NTf2]-). NMR and IR spectroscopy indicate that the electrostatic interactions are quite different from those in either [C2mim][OAc] or [C2mim][NTf2]. This is attributed to the ability of [OAc]- to form complexes with the [C2mim]+ ions at greater than 1:1 stoichiometries by drawing [C2mim]+ ions away from the less basic [NTf2]- ions. Solubility studies with molecular solvents (ethyl acetate, water) and pharmaceuticals (ibuprofen, diphenhydramine) show nonlinear trends as a function of ion content, which suggests that solubility can be tuned through changes in the ionic compositions.
- Wang, Hui,Kelley, Steven P.,Brantley, Jimmy W.,Chatel, Gregory,Shamshina, Julia,Pereira, Jorge F. B.,Debbeti, Varun,Myerson, Allan S.,Rogers, Robin D.
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p. 993 - 1002
(2015/04/14)
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- Efficient absorption of ammonia with hydroxyl-functionalized ionic liquids
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Ammonia (NH3) emitted from the ammonia synthesis process is a kind of waste chemical resource and a major environmental pollutant. The traditional water scrubbing method suffers from high energy consumption due to the concentrated NH3 from aqueous ammonia. Therefore, it is desirable to develop novel absorbents for the efficient, reversible and environmentally-friendly recovery of NH3. In this paper, a series of hydroxyl-functionalized imidazolium ILs ([EtOHmim]X, X = [NTf2], [PF6], [BF4], [DCA], [SCN] and [NO3]) were designed and prepared. Their physical properties and NH3 absorption capacities under different temperatures and pressures were systematically investigated. The effects of hydroxyl cation, anionic structures, pressure and temperature on absorption performance were sufficiently studied. In addition, the absorption mechanism was investigated in detail by spectral analysis and quantum chemistry calculations. Compared with conventional IL [Emim]X, a higher absorption capacity was achieved by introducing the hydroxyl group on the imidazolium cation. The mechanism results showed the fascinating absorption performance of the task-specific ILs was attributed to the stronger hydrogen bonding interaction between NH3 and the H atom of the hydroxyl group. Considering the excellent absorption performance, high thermal stability, and super reversibility, this type of IL provides great improvement over conventional IL and shows their enormous potential in NH3 recovery.
- Li, Zhijie,Zhang, Xiangping,Dong, Haifeng,Zhang, Xiaochun,Gao, Hongshuai,Zhang, Suojiang,Li, Jianwei,Wang, Congmin
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p. 81362 - 81370
(2015/10/06)
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- Eu3 + as a dual probe for the determination of IL anion donor power: A combined luminescence spectroscopic and electrochemical approach
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This work is aimed at giving proof that Eu(Tf2N)3 (Tf2N = bis(trifluoromethanesulfonyl)amide) can act as both an optical and electrochemical probe for the determination of the Lewis acidity of an ionic liquid anion. For that reason the luminescence spectra and cyclic voltammograms of dilute solutions of Eu(Tf2N)3 in various ionic liquids were investigated. The Eu2 +/3 + redox potential in the investigated ILs can be related to the Lewis basicity of the IL anion. The IL cation had little influence. The lower the determined halfwave potential, the higher the IL anion basicity. The obtained ranking can be confirmed by luminescence spectroscopy where a bathochromic shift of the 5D 0 → 7F4 transition indicates a stronger Lewis basicity of the IL anion.
- Babai, Arash,Kopiec, Gabriel,Lackmann, Anastasia,Mallick, Bert,Pitula, Slawomir,Tang, Sifu,Mudring, Anja-Verena
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p. 191 - 198
(2014/05/20)
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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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- Steric, hydrogen-bonding and structural heterogeneity effects on the nucleophilic substitution of N-(p-fluorophenyldiphenylmethyl)-4-picolinium chloride in ionic liquids
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The nucleophilic substitution of N-(p-fluorophenyldiphenylmethyl)-4- picolinium chloride was investigated using water and a range of alcoholic nucleophiles in ionic liquid solvents. The reactivity patterns across the nucleophiles examined could be attributed to steric factors, which mediated the relative nucleophilicities. Reducing the hydrogen-bond acidity of the ionic liquid cation was found to generally increase the rate of reaction, however, the magnitude of this rate effect could be influenced by the steric bulk of the nucleophile and the structural heterogeneity of the ionic liquid. Preferential solvation phenomena in binary mixtures of ionic liquids were examined and suggest that the mechanism behind the hydrogen-bond solvation phenomenon arises from direct cation-mediated, rather than indirect anion-mediated, effects. The Royal Society of Chemistry 2013.
- Weber, Cameron C.,Masters, Anthony F.,Maschmeyer, Thomas
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supporting information
p. 2534 - 2542
(2013/06/05)
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- Effect of ionic liquids on the conformation of a porphyrin-based viscometer
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Structure of the cationic and anionic counterparts of ionic liquids has a significant impact on the conformational bias of the porphyrin rotor; an apparent correlation between the conformation and the viscosity of ionic liquids was noted, albeit it was found to be distinct and more complex from that found in molecular solvents.
- Jameson, Laramie P.,Kimball, Joseph D.,Gryczynski, Zygmunt,Balaz, Milan,Dzyuba, Sergei V.
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p. 18300 - 18304
(2013/10/21)
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- Pseudo-encapsulation-nanodomains for enhanced reactivity in ionic liquids
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Domain constrained: Polar and nonpolar domains within 1-alkyl-3- methylimidazolium ionic liquids can affect reaction outcomes by pseudo-encapsulation of reactants and this has been explored for a nucleophilic substitution reaction using a cationic substrate and a range of nucleophiles. The significant rate enhancements observed correlate with the concentration of the polar reactants within the ionic liquid's polar domain. ([C nMIM]=1-alkyl-3-methylimidazolium). Copyright
- Weber, Cameron C.,Masters, Anthony F.,Maschmeyer, Thomas
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supporting information
p. 11483 - 11486
(2013/01/15)
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- Liquid-liquid interfacial tension of equilibrated mixtures of ionic liquids and hydrocarbons
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Ionic liquids are possible alternative solvents for the separation of aromatic and aliphatic hydrocarbons by liquid-liquid extraction. Interfacial tension is an important property to consider in the design of liquid-liquid extraction processes. In this work, the liquid-liquid interfacial tension and the mutual solubility at 25 °C have been measured for a series of biphasic, equilibrated mixtures of an ionic liquid and a hydrocarbon. In particular, the ionic liquids 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide (with the alkyl substituent being ethyl, hexyl or decyl), 1-ethyl-3- methylimidazolium ethylsulfate, and 1-ethyl-3-methylimidazolium methanesulfonate have been selected, as well as the hydrocarbons benzene, hexane, ethylbenzene, and octane. The selected sets of ionic liquids and hydrocarbons allow the analysis of the influence of a series of effects on the interfacial tension. For example, the interfacial tension decreases with an increase in the length of the alkyl substituent chain of the cation or with an increase of the degree of charge delocalisation in the anion of the ionic liquid. Also, the interfacial tension with the aromatic hydrocarbons is markedly lower than that with the aliphatic hydrocarbons. A smaller effect is caused by variation of the size of the hydrocarbon. Some of the observed trends can be explained from the mutual solubility of the hydrocarbon and the ionic liquid. Science China Press and Springer-Verlag Berlin Heidelberg 2012.
- Rodriguez, Hector,Arce, Alberto,Soto, Ana
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p. 1519 - 1524
(2012/11/07)
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- Synthetic organic electrochemistry in ionic liquids: The viscosity question
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Ionic liquids are obvious candidates for use in electrochemical applications due to their ionic character. Nevertheless, relatively little has been done to explore their application in electrosynthesis. We have studied the Shono oxidation of arylamines and carbamates using ionic liquids as recyclable solvents and have noted that the viscosity of the medium is a major problem, although with the addition of sufficient co-solvent, good results and excellent recovery and recycling of the ionic liquid can be achieved.
- Bornemann, Steven,Handy, Scott T.
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experimental part
p. 5963 - 5974
(2011/09/13)
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- Phase behavior and crystalline phases of ionic liquid-lithium salt mixtures with 1-alkyl-3-methylimidazolium salts
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The thermal phase behavior of 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (IM10 RTFSI where R = 1, 2, or 4 for methyl, ethyl or butyl, respectively) ionic liquid binary mixtures with LiTFSI have been investigated as models for electrolytes for lithium batteries. Diverse phase behavior is found with significant variations noted from similar mixtures in which the imidazolium cations are replaced with N-alkyl-N- methylpyrrolidinium cations. The crystal structure for a (1-x) IM 101TFSI-(x) LiTFSI (x = 0.50) (or 1/1 IM101TFSI/LiTFSI) phase is reported to further clarify the molecular level interactions occurring in these binary salt mixtures.
- Zhou, Qian,Fitzgerald, Kendall,Boyle, Paul D.,Henderson, Wesley A.
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experimental part
p. 1203 - 1208
(2011/10/09)
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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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- Transparent, flexible and highly conductive ion gels from ionic liquid compatible cyclic carbonate network
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Transparent, flexible, self-standing and highly ion conductive ion gels have been synthesised from novel ionic liquid compatible cyclic carbonate (CC) network polymer. The use of dual functional cyclic carbonate methacrylate (CCMA) monomer for the synthes
- Jana, Satyasankar,Parthiban, Anbanandam,Chai, Christina L. L.
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supporting information; experimental part
p. 1488 - 1490
(2010/06/12)
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- OXONIUM AND SULFONIUM SALTS
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The present invention relates to oxonium salts having [(Ro)3O]+ cations and sulfonium salts having [(Ro)3S]+ cations, where Ro denotes straight-chain or branched alkyl groups having 1-8 C atoms or phenyl which is unsubstituted or substituted by Ro, ORo, N(Ro)2, CN or halogen, and anions selected from the group of [PFx(CyF2y+1?zHz)6?x]? anions, where 2≦x≦5, 1≦y≦8 and 0≦z≦2y+1, or anions selected from the group of [BFn(CN)4?n]? anions, where n=0, 1 , 2 or 3, or anions selected from the group of [(Rf1SO2)2N]? anions or anions selected from the group of [BFwRf24?w]? anions, to processes for the preparation thereof, and to the use thereof, in particular for the preparation of ionic liquids.
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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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- A rationalization of the solvent effect on the Diels-Alder reaction in ionic liquids using multiparameter linear solvation energy relationships
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The Diels-Alder reaction between cyclopentadiene and three dienophiles (acrolein, methyl acrylate and acrylonitrile) having different hydrogen bond acceptor abilities has been carried out in several ionic liquids and molecular solvents in order to obtain information about the factors affecting reactivity and selectivity. The solvent effects on these reactions are examined using multiparameter linear solvation energy relationships. The collected data provide evidence that the solvent effects are a function of both the solvent and the solute. For a solvent effect to be seen, the solute must have a complimentary character; selectivities and rates are determined by the solvent hydrogen bond donation ability (α) in the reactions of acrolein and methyl acrylate, but not of acrylonitrile. The Royal Society of Chemistry 2008.
- Bini, Riccardo,Chiappe, Cinzia,Mestre, Veronica Llopsis,Pomelli, Christian Silvio,Welton, Thomas
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supporting information; experimental part
p. 2522 - 2529
(2009/02/02)
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- LCST-type liquid-liquid phase separation behaviour of poly(ethylene oxide) derivatives in an ionic liquid
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We present a new series of polymer-ionic liquid solutions exhibiting LCST-type liquid-liquid phase separation behaviour, and reveal their phase behaviour and intermolecular interactions based on phase diagrams and NMR analysis. The Royal Society of Chemistry.
- Tsuda, Ryohei,Kodama, Koichi,Ueki, Takeshi,Kokubo, Hisashi,Imabayashi, Shin-Ichiro,Watanabe, Masayoshi
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supporting information; experimental part
p. 4939 - 4941
(2009/06/06)
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- An acidity scale of 1,3-dialkylimidazolium salts in dimethyl sulfoxide solution
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(Chemical Equation Presented) Equilibrium acidities of 16 1,3-dialkylimidazolium-type ionic liquid (IL) molecules (1-16) were systematically measured by the overlapping indicator method at 25°C in dimethyl sulfoxide (DMSO) solution. The pKa values were observed to range from 23.4 for IL 12 to 19.7 for IL 6 (Tables 1 and 2), responding mainly to structural variations on the cation moiety. Excellent agreement between the spectrophotometrically determined pKa and that derived from NMR titration for 1,3,4,5-tetramethylimidazolium bis(trifluoromethanesulfonyl)imide (12) and the close match of the obtained pK values with the reported data in literature provide credence to the acidity measurements of the present work. The substituent effects at the imidazolium ring and the effects of counterions on the acidities of ionic liquids are discussed.
- Chu, Yuan,Deng, Hui,Cheng, Jin-Pei
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p. 7790 - 7793
(2008/02/13)
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- Ionic conducting gels, preparation method thereof and use of same
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A method of preparing an ionic conducting gel in solid form, known as ionogel. The method includes a step of mixing an ionic liquid with at least one molecular precursor containing at least one hydrolyzable group, if necessary in the presence of an acid, such as a carboxylic acid. The mixture is subsequently left to stand for one or more days until a gel is formed by polycondensation of the molecular precursor(s). The gel contains the aforementioned ionic liquid and can be set, in particular in transparent monolithic solid form.
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Page/Page column 4
(2008/06/13)
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- A thermoreversible ion gel by triblock copolymer self-assembly in an ionic liquid
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A new thermoreversible ion gel with high ionic conductivity was developed through the self-assembly of a triblock copolymer, by choosing appropriate associating end-blocks for the ionic liquid. The Royal Society of Chemistry.
- He, Yiyong,Lodge, Timothy P.
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p. 2732 - 2734
(2008/02/10)
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- How to predict the physical properties of ionic liquids: A volume-based approach
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(Chemical Equation Presented) The molecular volume Vm (that is, the sum of the ionic volumes Vion of the constituent ions) of an ionic liquid (IL) in combination with an anion-dependent empirical relationship is all one needs to predict physical properties such as viscosity, conductivity, and density of [N(CN)2]-, [BF4]-, [PF6]-, and [N(SO2CF3) 2]- ionic liquids, including those which may as yet only exist on paper.
- Slattery, John M.,Daguenet, Corinne,Dyson, Paul J.,Schubert, Thomas J. S.,Krossing, Ingo
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p. 5384 - 5388
(2008/03/15)
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- 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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p. 1475 - 1482
(2007/10/03)
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- IONIC COMPOUND
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PROBLEM TO BE SOLVED: To provide a salt melting at normal temperature, exhibiting a low-viscosity liquid shape at room temperature, having sufficiently high electroconductivity, and useful as an electrolyte or electrolysis solution for an electrochemical device such as a secondary battery, an electric double layer capacitor, a fuel battery, and a dye-sensitized solar battery, or a solvent for organic synthesis. SOLUTION: The ionic compound is represented by formula (1): C+A- (1) [wherein, A- is an anion represented by structural formula (2): FSO2-N(-)-SO2CnF2n+1 or structural formula (3): FSO2-N(-)-COCnF2n+1 {in structural formulas (2) and (3), n is an integer of 1-5}; C+ is a cation represented by formulas (4), (5), (6), (7), (8), (9), (10) or (11) {in general formulas (4) to (8), R1 to R6 are each independently a hydrogen atom, a halogen atom, a 1-5C alkyl group, an aralkyl group, an alkynyl group or an alkoxyalkyl group} and {in general formulas (9) to (11), R1 to R4 are each independently a 1-6C alkyl group, an aralkyl group, an alkynyl group or an alkoxyalkyl group; with the proviso that any two groups in R1 to R4 may form a ring by bonding to each other}].
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(2008/06/13)
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