TY - JOUR A1 - Balischewski, Christian A1 - Bhattacharyya, Biswajit A1 - Sperlich, Eric A1 - Günter, Christina A1 - Beqiraj, Alkit A1 - Klamroth, Tillmann A1 - Behrens, Karsten A1 - Mies, Stefan A1 - Kelling, Alexandra A1 - Lubahn, Susanne A1 - Holtzheimer, Lea A1 - Nitschke, Anne A1 - Taubert, Andreas T1 - Tetrahalidometallate(II) ionic liquids with more than one metal BT - the effect of bromide versus chloride JF - Chemistry - a European journal N2 - Fifteen N-butylpyridinium salts - five monometallic [C4Py](2)[MBr4] and ten bimetallic [C4Py](2)[(M0.5M0.5Br4)-M-a-Br-b] (M=Co, Cu, Mn, Ni, Zn) - were synthesized, and their structures and thermal and electrochemical properties were studied. All the compounds are ionic liquids (ILs) with melting points between 64 and 101 degrees C. Powder and single-crystal X-ray diffraction show that all ILs are isostructural. The electrochemical stability windows of the ILs are between 2 and 3 V. The conductivities at room temperature are between 10(-5) and 10(-6) S cm(-1). At elevated temperatures, the conductivities reach up to 10(-4) S cm(-1) at 70 degrees C. The structures and properties of the current bromide-based ILs were also compared with those of previous examples using chloride ligands, which illustrated differences and similarities between the two groups of ILs. KW - electrochemistry KW - ionic liquids KW - metal-containing ionic liquids; KW - N-butylpyridinium bromide KW - tetrahalidometallates Y1 - 2022 U6 - https://doi.org/10.1002/chem.202201068 SN - 1521-3765 VL - 28 IS - 64 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Balischewski, Christian A1 - Behrens, Karsten A1 - Zehbe, Kerstin A1 - Günter, Christina A1 - Mies, Stefan A1 - Sperlich, Eric A1 - Kelling, Alexandra A1 - Taubert, Andreas T1 - Ionic liquids with more than one metal BT - optical and rlectrochemical properties versus d-block metal vombinations JF - Chemistry - a European journal N2 - Thirteen N-butylpyridinium salts, including three monometallic [C4Py](2)[MCl4], nine bimetallic [C4Py](2)[(M1-xMxCl4)-M-a-Cl-b] and one trimetallic compound [C4Py](2)[(M1-y-zMyMz (c) Cl4)-M-a-M-b] (M=Co, Cu, Mn; x=0.25, 0.50 or 0.75 and y=z=0.33), were synthesized and their structure and thermal and electrochemical properties were studied. All compounds are ionic liquids (ILs) with melting points between 69 and 93 degrees C. X-ray diffraction proves that all ILs are isostructural. The conductivity at room temperature is between 10(-4) and 10(-8) S cm(-1). Some Cu-based ILs reach conductivities of 10(-2) S cm(-1), which is, however, probably due to IL dec. This correlates with the optical bandgap measurements indicating the formation of large bandgap semiconductors. At elevated temperatures approaching the melting points, the conductivities reach up to 1.47x10(-1) S cm(-1) at 70 degrees C. The electrochemical stability windows of the ILs are between 2.5 and 3.0 V. KW - bandgap KW - electrochemistry KW - ionic liquids KW - metal-containing ionic KW - liquids KW - tetrahalido metallates Y1 - 2020 U6 - https://doi.org/10.1002/chem.202003097 SN - 0947-6539 SN - 1521-3765 VL - 26 IS - 72 SP - 17504 EP - 17513 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Taubert, Andreas A1 - Löbbicke, Ruben A1 - Kirchner, Barbara A1 - Leroux, Fabrice T1 - First examples of organosilica-based ionogels BT - synthesis and electrochemical behavior JF - Beilstein journal of nanotechnology N2 - The article describes the synthesis and properties of new ionogels for ion transport. A new preparation process using an organic linker, bis(3-(trimethoxysilyl) propyl) amine (BTMSPA), yields stable organosilica matrix materials. The second ionogel component, the ionic liquid 1-methyl-3-(4-sulfobutyl) imidazolium 4-methylbenzenesulfonate, [BmimSO(3)H][PTS], can easily be prepared with near-quantitative yields. [BmimSO(3)H][PTS] is the proton conducting species in the ionogel. By combining the stable organosilica matrix with the sulfonated ionic liquid, mechanically stable, and highly conductive ionogels with application potential in sensors or fuel cells can be prepared. KW - ionic liquids KW - ionogels KW - organosilica KW - proton conductivity Y1 - 2017 U6 - https://doi.org/10.3762/bjnano.8.77 SN - 2190-4286 VL - 8 SP - 736 EP - 751 PB - Beilstein-Institut zur Förderung der Chemischen Wissenschaften CY - Frankfurt, Main ER - TY - JOUR A1 - Zehbe, Kerstin A1 - Kollosche, Matthias A1 - Lardong, Sebastian A1 - Kelling, Alexandra A1 - Schilde, Uwe A1 - Taubert, Andreas T1 - Ionogels Based on Poly(methyl methacrylate) and Metal-Containing Ionic Liquids: Correlation between Structure and Mechanical and Electrical Properties JF - International journal of molecular sciences N2 - Ionogels (IGs) based on poly(methyl methacrylate) (PMMA) and the metal-containing ionic liquids (ILs) bis-1-butyl-3-methlimidazolium tetrachloridocuprate(II), tetrachloride cobaltate(II), and tetrachlorido manganate(II) have been synthesized and their mechanical and electrical properties have been correlated with their microstructure. Unlike many previous examples, the current IGs show a decreasing stability in stress-strain experiments on increasing IL fractions. The conductivities of the current IGs are lower than those observed in similar examples in the literature. Both effects are caused by a two-phase structure with micrometer-sized IL-rich domains homogeneously dispersed an IL-deficient continuous PMMA phase. This study demonstrates that the IL-polymer miscibility and the morphology of the IGs are key parameters to control the (macroscopic) properties of IGs. KW - microstructure KW - ionogels KW - ionic liquids KW - phase separation KW - mechanical properties KW - ionic conductivity Y1 - 2016 U6 - https://doi.org/10.3390/ijms17030391 SN - 1422-0067 VL - 17 PB - MDPI CY - Basel ER - TY - JOUR A1 - Mondal, Suvendu Sekhar A1 - Bhunia, Asamanjoy A1 - Attallah, Ahmed G. A1 - Matthes, Philipp R. A1 - Kelling, Alexandra A1 - Schilde, Uwe A1 - Müller-Buschbaum, Klaus A1 - Krause-Rehberg, Reinhard A1 - Janiak, Christoph A1 - Holdt, Hans-Jürgen T1 - Study of the Discrepancies between Crystallographic Porosity and Guest Access into Cadmium-Imidazolate Frameworks and Tunable Luminescence Properties by Incorporation of Lanthanides JF - Chemistry - a European journal N2 - An extended member of the isoreticular family of metal-imidazolate framework structures, IFP-6 (IFP=imidazolate framework Potsdam), based on cadmium metal and an in situ functionalized 2-methylimidazolate-4-amide-5-imidate linker is reported. A porous 3D framework with 1D hexagonal channels with accessible pore windows of 0.52nm has been synthesized by using an ionic liquid (IL) linker precursor. IFP-6 shows significant gas uptake capacity only for CO2 and CH4 at elevated pressure, whereas it does not adsorb N-2, H-2, and CH4 under atmospheric conditions. IFP-6 is assumed to deteriorate at the outside of the material during the activation process. This closing of the metal-organic framework (MOF) pores is proven by positron annihilation lifetime spectroscopy (PALS), which revealed inherent crystal defects. PALS results support the conservation of the inner pores of IFP-6. IFP-6 has also been successfully loaded with luminescent trivalent lanthanide ions (Ln(III)=Tb, Eu, and Sm) in a bottom-up one-pot reaction through the in situ generation of the linker ligand and in situ incorporation of photoluminescent Ln ions into the constituting network. The results of photoluminescence investigations and powder XRD provide evidence that the Ln ions are not doped as connectivity centers into the frameworks, but are instead located within the pores of the MOFs. Under UV light irradiation, Tb@IFP-6 and Eu@IFP-6 ((exc)=365nm) exhibit observable emission changes to a greenish and reddish color, respectively, as a result of strong Ln 4f emissions. KW - adsorption KW - cadmium KW - ionic liquids KW - luminescence KW - metal-organic frameworks Y1 - 2016 U6 - https://doi.org/10.1002/chem.201504757 SN - 0947-6539 SN - 1521-3765 VL - 22 SP - 6905 EP - 6913 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Mondal, Suvendu Sekhar A1 - Mueller, Holger A1 - Junginger, Matthias A1 - Kelling, Alexandra A1 - Schilde, Uwe A1 - Strehmel, Veronika A1 - Holdt, Hans-Jürgen T1 - Imidazolium 2-substituted 4,5-dicyanoimidazolate ionic liquids: synthesis, crystal structures and structure-thermal property relationships JF - Chemistry - a European journal N2 - Thirty six novel ionic liquids (ILs) with 1-butyl-3-methylimidazolium and 3-methyl-1-octylimidazolium cations paired with 2-substitited 4,5-dicyanoimidazolate anions (substituent at C2=chloro, bromo, methoxy, vinyl, amino, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and phenyl) have been synthesized and characterized by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and single-crystal X-ray crystallography. The effects of cation and anion type and structure on the thermal properties of the resulting ionic liquids, including several room temperature ionic liquids (RTILs) are examined and discussed. ILs exhibited large liquid and crystallization ranges and formed glasses on cooling with glass transition temperatures in the range of -22 to -68 degrees C. The effects of alkyl substituents of the imidazolate anion reflected the crystallization, melting points and thermal decomposition of the ILs. The Coulombic packing force, van der Waals forces and size of the anions can be considered for altering the thermal transitions. Three crystal structures of the ILs were determined and the effects of changes to the cations and anions on the packing of the structure were investigated. KW - crystal structures KW - imidazole KW - ion exchange KW - ionic liquids KW - pi-pi stacking Y1 - 2014 U6 - https://doi.org/10.1002/chem.201304934 SN - 0947-6539 SN - 1521-3765 VL - 20 IS - 26 SP - 8170 EP - 8181 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Xie, Zai-Lai A1 - Taubert, Andreas T1 - Thermomorphic behavior of the ionic liquids [C(4)mim][FeCl4] and [C(12)mim][FeCl4] JF - ChemPhysChem : a European journal of chemical physics and physical chemistry N2 - The iron-containing ionic liquids 1-butyl-3-methylimidazolium tetrachloroferrate(III) [C(4)mim][FeCl4] and 1-dodecyl-3-methylimidazolium tetrachloroferrate(III) [C(12)mim][FeCl4] exhibit a thermally induced demixing with water (thermomorphism). The phase separation temperature varies with IL weight fraction in water and can be tuned between 100 degrees C and room temperature. The reversible lower critical solution temperature (LCST) is only observed at IL weight fractions below ca. 35% in water. UV/Vis, IR, and Raman spectroscopy along with elemental analysis prove that the yellow-brown liquid phase recovered after phase separation is the starting IL [C(4)mim][FeCl4] and [C(12)mim][FeCl4], respectively. Photometry and ICP-OES show that about 40% of iron remains in the water phase upon phase separation. Although the process is thus not very efficient at the moment, the current approach is the first example of an LCST behavior of a metal-containing IL and therefore, although still inefficient, a prototype for catalyst removal or metal extraction. KW - imidazolium KW - ionic liquids KW - phase transitions KW - Raman spectroscopy KW - thermomorphism Y1 - 2011 U6 - https://doi.org/10.1002/cphc.201000808 SN - 1439-4235 VL - 12 IS - 2 SP - 364 EP - 368 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Taubert, Andreas A1 - Stange, Franziska A1 - Li, Zhonghao A1 - Junginger, Mathias A1 - Günter, Christina A1 - Neumann, Mike A1 - Friedrich, Alwin T1 - CuO nanoparticles from the Strongly Hydrated Ionic Liquid Precursor (ILP) Tetrabutylammonium Hydroxide evaluation of the Ethanol Sensing Activity JF - ACS applied materials & interfaces N2 - The sensing potential of CuO nanoparticles synthesized via. precipitation from a water/ionic liquid precursor (ILP) mixture was investigated. The particles have a moderate surface area of 66 m(2)/g after synthesis, which decreases upon thermal treatment to below 5 m(2)/g. Transmission electron microscopy confirms crystal growth upon annealing, likely due to sintering effects. The as-synthesized particles can be used for ethanol sensing. The respective sensors show fast response and recovery times of below 10 s and responses greater than 2.3 at 100 ppm of ethanol at 200 degrees C, which is higher than any CuO-based ethanol sensor described so far. KW - ionic liquids KW - ionic liquid precursors KW - tetrabutylammonium hydroxide KW - nanoparticles KW - CuO KW - gas sensing Y1 - 2012 U6 - https://doi.org/10.1021/am201427q SN - 1944-8244 VL - 4 IS - 2 SP - 791 EP - 795 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Dolya, Natalya A1 - Rojas, Oscar A1 - Kosmella, Sabine A1 - Tiersch, Brigitte A1 - Koetz, Joachim A1 - Kudaibergenov, Sarkyt T1 - "One-Pot" in situ frmation of Gold Nanoparticles within Poly(acrylamide) Hydrogels JF - Macromolecular chemistry and physics N2 - This paper focuses on two different strategies to incorporate gold nanoparticles (AuNPs) into the matrix of polyacrylamide (PAAm) hydrogels. Poly(ethyleneimine) (PEI) is used as both reducing and stabilizing agent for the formation of AuNPs. In addition, the influence of an ionic liquid (IL) (i.e., 1-ethyl-3-methylimidazolium ethylsulfate) on the stability of the nanoparticles and their immobilization in the hydrogel is investigated The results show that AuNPs surrounded by a shell containing PEI and IL, synthesized according to the one-pot approach, are much better immobilized within the PAAm hydrogel. Hereby, the IL is responsible for structural changes in the hydrogel as well as the improved stabilization and embedding of the AuNPs into the polymer gel matrix. KW - gold nanoparticles KW - immobilization KW - ionic liquids KW - poly(acrylamide) hydrogels Y1 - 2013 U6 - https://doi.org/10.1002/macp.201200727 SN - 1022-1352 VL - 214 IS - 10 SP - 1114 EP - 1121 PB - Wiley-VCH CY - Weinheim ER -