Ionic liquids that form adducts with alcohols

Ionic liquids bearing an activated carbonyl group in the cation are shown to form adducts with alcohols without the aid of any catalysts. How these functionalised ionic liquids could be used in altering vapour phase compositions of alcohols and in alcohol separations are demonstrated.</p

Graz. Wetterkugel und Kastell am Schlossberg. Fohes Neujahr!

Ehemalige Wetterkugel auf der Kanonenbaste

Ionic Liquids–Cobalt(II) Thermochromic Complexes: How the Structure Tunability Affects “Self-Contained” Systems

With the aim of obtaining thermochromic systems with potential applications in solar energy storage, we evaluated the behavior of some sugar-based ionic liquids (ILs) 12Co(NTf2)2 complexes, in IL solution, as a function of temperature. Different structural changes on the cation, the nature of the anion, and the nature of the IL used as the solvent were considered. The analysis of the above factors was carried out through a combined approach of different techniques, that is, variable temperature UV 12vis and NMR spectroscopies, conductivity, and thermal gravimetric analysis. The thermochromic systems were analyzed both as solutions and as thin films, and the data collected highlight the defining role played by both the cation structure and the solvent nature in determining their performance. Most of the investigated systems show a chromogenic transition from pink to blue, occurring in a temperature range suitable for practical applications (40 1260 \ub0C). Interestingly, when embedded in a polymeric matrix, thin films with high recyclability and long life are also described

Dissolution and speciation of arsenic oxides in ionic liquids

C

3-Methylpiperidinium ionic liquids

[EN] A wide range of room temperature ionic liquids based on the 3-methylpiperdinium cation core were produced from 3-methylpiperidine, which is a derivative of DYTEKs (R) A amine. First, reaction with 1-bromoalkanes or 1-bromoalkoxyalkanes generated the corresponding tertiary amines (Rm beta pip, R = alkyl or alkoxyalkyl); further quaternisation reactions with the appropriate methylating agents yielded the quaternary [Rmm(beta)pip]X salts (X-= I-, [CF3CO2]-or [OTf](-); Tf = -SO2CF3), and [Rmm(beta)pip][NTf2] were prepared by anion metathesis from the corresponding iodides. All [NTf2]-salts are liquids at room temperature. [Rmm(beta)pip]X (X-= I-, [CF3CO2]-or [OTf](-)) are low-melting solids when R = alkyl, but room temperature liquids upon introduction of ether functionalities on R. Neither of the 3-methylpiperdinium ionic liquids showed any signs of crystallisation, even well below 0 degrees C. Some related non-C-substituted piperidinium and pyrrolidinium analogues were prepared and studied for comparison. Crystal structures of 1-hexyl-1,3-dimethylpiperidinium tetraphenylborate, 1-butyl-3-methylpiperidinium bromide, 1-(2-methoxyethyl)1- methylpiperidinium chloride and 1-(2-methoxyethyl)-1-methylpyrrolidinium bromide are reported. Extensive structural and physical data are collected and compared to literature data, with special emphasis on the systematic study of the cation ring size and/or asymmetry effects on density, viscosity and ionic conductivity, allowing general trends to be outlined. Cyclic voltammetry shows that 3-methylpiperidinium ionic liquids, similarly to azepanium, piperidinium or pyrrolidinium counterparts, are extremely electrochemically stable; the portfolio of useful alternatives for safe and high-performing electrolytes is thus greatly extended.We would like to acknowledge the EPSRC NCS in Southampton for the single crystal X-ray diffraction data collection and INVISTA Intermediates for funding.Belhocine, T.; Forsyth, SA.; Gunaratne, HQN.; Nieuwenhuyzen, M.; Nockemann, P.; Vaca Puga, A.; Seddon, KR.... (2015). 3-Methylpiperidinium ionic liquids. Physical Chemistry Chemical Physics. 17(16):10398-10416. doi:10.1039/C4CP05936KS10398104161716C. Mikolajczak , M.Kahn, K.White and R. T.Long, Lithium-ion Batteries Hazard and Use Assessment, Springer, New York, 2012Choi, N.-S., Chen, Z., Freunberger, S. A., Ji, X., Sun, Y.-K., Amine, K., … Bruce, P. G. (2012). Challenges Facing Lithium Batteries and Electrical Double-Layer Capacitors. 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V., … Whiston, K. (2011). Azepanium ionic liquids. Green Chemistry, 13(11), 3137. doi:10.1039/c1gc15189dPandey, G., Devi Reddy, G., & Kumaraswamy, G. (1994). Photoinduced electron transfer (PET) promoted cyclisations of 1-[N-alkyl-N-(trimethylsilyl)methyl]amines tethered to proximate olefin: mechanistic and synthetic perspectives. Tetrahedron, 50(27), 8185-8194. doi:10.1016/s0040-4020(01)85300-xPandey, G., Kumaraswamy, G., & Bhalerao, U. . (1989). Photoinduced set generation of α-amineradicals : A practical method for the synthesis of pyrrolidines and piperidines. Tetrahedron Letters, 30(44), 6059-6062. doi:10.1016/s0040-4039(01)93854-7A. J. Carmichael , M.Deetlefs, M. J.Earle, U.Fröhlich and K. R.Seddon, in Ionic Liquids as Green Solvents: Progress and Prospects, ed. R. D. Rogers and K. R. Seddon, American Chemical Society, Washington, DC, 2003, pp. 14–31Fang, S., Zhang, Z., Jin, Y., Yang, L., Hirano, S., Tachibana, K., & Katayama, S. (2011). 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An improved method to measure the rate of vaporisation and thermal decomposition of high boiling organic and ionic liquids by thermogravimetrical analysis. Physical Chemistry Chemical Physics, 12(38

1‐(+)‐Dehydroabietylimidazolium Salts as Enantiomer Discriminators for NMR Spectroscopy

Nine new (+)-dehydroabietylimidazolium salts were synthesised and studied as chiral solvating agents for several different racemic aromatic and non-aromatic carboxylate salts. These cationic chiral solvating agents resolve racemic ionic analytes better than non-ionic ones. Bis(dehydroabietylimidazolium) bis(trifluoromethanesulfonimide) gave the best discrimination for the enantiomers of carboxylate salts. Its resolution behaviour was studied by an NMR titration experiment, which indicated 1 : 1 complexation with the racemic analyte. The dehydroabietylimidazolium salts were also useful in enantiomeric excess (ee) determinations, and for the recognition of chirality of racemic aromatic and non-aromatic α-substituted carboxylic acids. </jats:p

Enhanced laccase stability through mediator partitioning into hydrophobic ionic liquids

Partitioning mediators into water-immiscible ionic liquids protects laccase from inactivation.</p

Ionic liquids for efficient hydrogen sulfide and thiol scavenging

Functionalised pyridinium and ammonium ionic liquids bearing a Michael acceptor are shown to scavenge H2S gas and various thiols, in most cases, without the aid of any added bases. Utilising the effective non-volatility of ionic liquids and ‘tagging’ malodourous substances to an ionic matrix renders them odourless.</p