Cover Pictures

Open Access

Front Cover: Metal Assisted Synthesis of Cationic Sulfidobismuth Cubanes in Ionic Liquids (ChemistryOpen 2/2021)

  • Pages: 56
  • First Published: 09 February 2021
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The Front Cover shows the spiro-dicubane Bi7S85+ in the center, accompanied by two Bi4S44+ hetero-cubanes on both sides, which are shown along their threefold axis. These sulfidobismuth polycations were isolated in salts with [AlCl4] and [S(AlCl3)3]2– anions. The starting material was Bi2S3, which is generally hard to dissolve but can easily be activated under ionothermal conditions. Moreover, the presence of noble metal ions, such as Ag+, Au+ or Pt2+, played a crucial role for the formation of those compounds. This research was performed in the framework of the Priority Program SPP 1708 “Material Synthesis Near Room Temperature” of the German Research Council (DFG). More information can be found in the Full Paper by Maximilian Knies et al.

Open Access

Cover Feature: Reactivity of Ionic Liquids: Reductive Effect of [C4C1im]BF4 to Form Particles of Red Amorphous Selenium and Bi2Se3 from Oxide Precursors (ChemistryOpen 2/2021)

  • Pages: 57
  • First Published: 10 February 2021
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The Cover Feature shows the correlation between the stability and reactivity of ionic liquids (ILs). Undercutting the maximum operating temperature (MOT) the IL initially is protected. Reaching the MOT, reactive species can be formed by thermal decomposition and functionality of the IL changes. Thus IL, actually used as a solvent, can become reactants. A current case study shows, that, exceeding the calculated MOT, reactive decomposition products of [C4C1im]BF4 lead to the reduction of the oxide precursor SeO2 and the formation of red amorphous selenium. Analyzing the gaseous species formed during the reaction, the reaction mechanism can be deduced similar to Riley oxidation. Thereby, but-1-ene, reacts with SeO2 to Se, H2O, and but-3-en-2-one. Concluding, the suitability of the single-source oxide precursor Bi2Se3O9 for the synthesis of Bi2Se3 is proven. More information can be found in the Full Paper by Monika Knorr et al.

Cover Profile

Open Access

Metal Assisted Synthesis of Cationic Sulfidobismuth Cubanes in Ionic Liquids

  • Pages: 59
  • First Published: 10 February 2021
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“…This study emphasizes the importance of various reaction parameters on the outcome of syntheses in ionic liquids…” Find out more about the story behind the front cover research at 10.1002/open.202000246.

Editorial

Open Access

Materials Synthesis in Ionic Liquids

  • Pages: 60-61
  • First Published: 10 February 2021
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Synthesis near room temperature: Michael Ruck, chair of the priority program “Synthesis near Room-Temperature” (SPP 1708) of the German Research Foundation (DFG), describes the work carried out within the frame of this research program since its establishment in 2014.

Reviews

Open Access

Pseudohalogen Chemistry in Ionic Liquids with Non-innocent Cations and Anions

  • Pages: 62-71
  • First Published: 10 November 2020
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The reaction of ionic liquids (ILs) with methylcarbonate anions like [R3MeE][CO3Me] (E=N: R=Et, nPr, nBu; E=P, R=Ph) with Me3Si−X (X=CN, N3, OCN, SCN) or H2SiF6 led to quantitative formation of pseudohalide salts [R3MeE]X or fluorosilicates, e. g. [R3MeN]2[SiF6]. From these precursors, novel anionic species like [B(OMe)3(CN)] or cyanido(halido)silicates of the type [SiCl0.78(CN)5.22]2−, [SiF(CN)5]2− and [Si(CN)6]2− were obtained. Functionalization of the hexacyanidosilicate with the Lewis acid B(C6F5)3 led to the voluminous WCA {Si[CN⋅B(C6F5)3]6}2−. Beside [H(NCS)2], highly labile solvate anions of the type [X(HCN)2] (X=CN, SCN), [X(HCN)3] (X=CN, N3, OCN) and [P(CN⋅HCN)2] were obtained from IL-like mixtures, when starting from [WCC]X ([WCC]=[Ph4P], [PPN]) and neat HCN.

Open Access

Understanding the Photoexcitation of Room Temperature Ionic Liquids

  • Pages: 72-82
  • First Published: 03 December 2020
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Room temperature ionic liquids have become of major interest in various applications. Therefore, a thorough physico-chemical understanding of the pure solvent property and in chemical reactions is mandatory. This minireview focuses on recent advances in detecting transient species after photoexcitation and following its dynamics to get a deeper insight into elementary steps.

Full Papers

Open Access

Chalcogenido-Dimethylgallates and -Indates DMPyr2[Me2M(μ2−E)]2 (M=Ga, In; E=S, Se): Building Blocks for Higher and Lower Order Chalcogenidoindates

  • Pages: 83-91
  • First Published: 10 February 2021
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Thermodynamics in action! Condensation of Me3Ga and Me3In with anions [EH] (E=S, Se) to four-membered rings, their cleavage or expansion and condensation to a cluster with inverse adamantane structure is driven by methane elimination, charge delocalization and dissociation.

Reviews

Open Access

Heavy Chalcogenide-Based Ionic Liquids in Syntheses of Metal Chalcogenide Materials near Room Temperature

  • Pages: 92-96
  • First Published: 10 February 2021
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Low temperature materials syntheses: Ionic liquids with highly reactive anions [E-SiMe3] and [E−H] (E=S, Se, Te) are valuable synthons for the synthesis of chalcogenido metalates Cat+[M(E-SiMe3)n] and Catn[RmM(E)]n serving as thermally metastable precursors in binary and multinary metal chalcogenide materials preparation.

Full Papers

Open Access

Speciation of Copper(II)-Betaine Complexes as Starting Point for Electrochemical Copper Deposition from Ionic Liquids

  • Pages: 97-109
  • First Published: 01 December 2020
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The influence of reaction parameters of the dissolution of copper(II) oxide in the ionic [Hbet][NTf2] and on the speciation of coordination compounds is investigated. The applicability to electrochemical copper deposition, especially the copper plating of steel, is shown.

Open Access

Metal Assisted Synthesis of Cationic Sulfidobismuth Cubanes in Ionic Liquids

  • Pages: 110-116
  • First Published: 19 October 2020
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Two new compounds containing sulfidobismuth cubane or spiro-dicubane cations were obtained from metal assisted ionothermal syntheses. Fine-tuning of the composition of the reaction mixture including the ionic liquid proved to be essential for successful syntheses.

Open Access

Low Temperature Activation of Tellurium and Resource-Efficient Synthesis of AuTe2 and Ag2Te in Ionic Liquids

  • Pages: 117-124
  • First Published: 19 October 2020
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Ag2Te and AuTe2 were obtained from the elements in the ionic liquid [P66614]Cl at room temperature. The reaction is driven by a dissolved tellurium species that reacts with the noble metal. In commercial [P66614]Cl, tellurium is reduced by trialkylphosphane impurities. A purification protocol was developed to suspend the influence of the trialkylphosphane. In the purified medium, a different tellurium species appears.

Open Access

Reactivity of Ionic Liquids: Reductive Effect of [C4C1im]BF4 to Form Particles of Red Amorphous Selenium and Bi2Se3 from Oxide Precursors

  • Pages: 125-140
  • First Published: 16 December 2020
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Exceeding the thermal stability of [C4C1im]BF4, the formation of the decomposition product but-1-ene leads to the reduction of SeO2 and the formation of but-3-en-2-one, H2O, and amorphous red selenium without the addition of an external reducing agent. This reduction behavior can also be observed using the single source oxide precursor Bi2Se3O9 resulting in the formation of Bi2Se3.

Open Access

Model Studies on the Ozone-Mediated Synthesis of Cobalt Oxide Nanoparticles from Dicobalt Octacarbonyl in Ionic Liquids

  • Pages: 141-152
  • First Published: 18 September 2020
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Low-temperature & Co.: We investigate the ozone-mediated preparation of CoxOy in an IL under UHV to study interactions between the reactants by varying deposition order and temperature of the system. We show that the IL and initially formed CoxOy layer protect the precursor against oxidation. This effect is lost at elevated temperatures

Open Access

Tetrahydrothiophene-Based Ionic Liquids: Synthesis and Thermodynamic Characterizations

  • Pages: 153-163
  • First Published: 23 December 2020
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The synthesis of S-alkyl tetrahydrothiophenium, [CnTHT]+ tetraphenylborate, [BPh4] salts and bis(trifluorosulfonyl)imide, [NTf2] ionic liquids (ILs) is described. For the ILs, densities, viscosities, vapor pressures and water solubilities were determined and modelled using PC-SAFT for the first time.

Open Access

Statistic Replacement of Lanthanide Ions in Bis-salicylatoborate Coordination Polymers for the Deliberate Control of the Luminescence Chromaticity

  • Pages: 164-170
  • First Published: 25 January 2021
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Luminescence chromaticity tuning between green, yellow and red was achieved by statistic replacement of Eu3+ and Tb3+ in the coordination polymers 1[EuxTb1−x(BSB)3(py)2], (x=0.25–0.75), containing the bis-salicylatoborate anion.

Open Access

Ge−Fe Carbonyl Cluster Compounds: Ionic Liquids-Based Synthesis, Structures, and Properties

  • Pages: 171-180
  • First Published: 23 November 2020
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Nine Ge−Fe carbonyl cluster compounds are prepared via ionic liquids-based synthesis, which allows to identify the essential experimental parameters and to compare the structural motifs and the stability of the compounds.

Open Access

Synthesis of Ti(OH)OF ⋅ 0.66 H2O in Imidazolium-based Ionic Liquids

  • Pages: 181-188
  • First Published: 26 November 2020
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Under the influence: In this study the influence of the alkyl chain lengths of imidazolium-based ionic liquids (ILs) on the a low-temperature synthesis of Ti(OH)OF ⋅ 0.66 H2O and TiO2(B) nanoparticles is investigated.

Open Access

Influence of Nanoparticle Processing on the Thermoelectric Properties of (BixSb1−X)2Te3 Ternary Alloys

  • Pages: 189-198
  • First Published: 25 January 2021
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Tetradymite-type ternary (BixSb1-x)2Te3 (x=0.25, 0.5, 0.75) nanoparticles were synthesized in an ionic-liquid approach. The effect of thermal annealing on the chemical composition and morphology of the nanoparticles as well as their transport properties prior and after annealing is reported.

Open Access

Volatility of molten salts [Ph4P][NTf2] and Cs[NTf2]

  • Pages: 199-204
  • First Published: 16 December 2020
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The volatility of ionic liquids is not negligible at elevated temperatures. It is related to vapor pressures. We report the precise absolute vapor pressures and enthalpies of vaporization, of [Ph4P][NTf2] and Cs[NTf2], which were measured using the quartz-crystal microbalance (QCM) method. Volatilities of both compounds is significantly lower compared to commonly used [Cnmim][NTf2] These values are useful for catalytic applications of ionic liquid as well as for qualitative assessment solubilities of ionic compounds in common ionic liquids of practical importance.

Open Access

Reactivity and Controlled Redox Reactions of Salt-like Intermetallic Compounds in Imidazolium-Based Ionic Liquids

  • Pages: 205-215
  • First Published: 25 January 2021
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High-purity 1,2,3-trisubstituted imidazolium [TFSI] ionic liquids were prepared and found inert towards the redox-sensitive Na12Ge17, making them suitable media for heterogeneous redox reactions. By admixture of benzophenone, Na12Ge17 was oxidized to an X-ray amorphous product, which proved valuable as a precursor for a thermal conversion to the difficult to access type-II clathrate Na24–δGe136 with almost completely Na-filled polyhedral cages.

Open Access

Extremely Low Vapor-Pressure Data as Access to PC-SAFT Parameter Estimation for Ionic Liquids and Modeling of Precursor Solubility in Ionic Liquids

  • Pages: 216-226
  • First Published: 25 January 2021
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The conventional way to fit ionic liquid parameters of equations of state to density is compared using a new method. The experimental vapor pressures as well as the density have been used as input to the model parameter estimation. The work was performed within the framework of the EOS PC-SAFT (perturbed-chain statistical associating fluid theory). The new method allows modeling density and vapor pressure accurately, and still allows for an improved modeling of the solubility of precursors in ionic liquids.

Open Access

Ionic Liquid-Driven Formation of and Cation Exchange in Layered Sulfido Stannates – a CH2 Group Makes the Difference

  • Pages: 227-232
  • First Published: 19 November 2020
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Salts of layered sulfido stannate anions are obtained by ionothermal treatment of K4[SnS4] ˙ 4H2O comprising tetrahedral [SnS4]4− anions. The products form selectively upon choosing a specific pair of temperature and ionic liquid, and they can be obtained in large scale in phase pure form. Moreover, post-synthetic treatment of one compound with the ionic liquid of the other one causes fast cation exchange under formation of the other network.

Open Access

UiO-66 and hcp UiO-66 Catalysts Synthesized from Ionic Liquids as Linker Precursors

  • Pages: 233-242
  • First Published: 16 December 2020
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The use of ionic liquids as linker precursor for the synthesis of the metal-organic frameworks hcp and fcc UiO-66 results in faster crystallization thereby reducing synthesis time and energy consumed. Furthermore, the catalytic activity of the MOFs in the cyclization of citronellal to isopulegol is increased due to defects within the frameworks while the selectivity is not affected.

Open Access

In the footsteps of August Michaelis: Syntheses and Thermodynamics of Extremely Low-Volatile Ionic Liquids

  • Pages: 243-247
  • First Published: 23 December 2020
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Finding the right H: An accurate determination of the vaporisation enthalpy is crucial given the use of low-volatile ionic liquids for industrial applications, These values have been determined for nine known ionic liquids, five of which contain the thermally extreme robust tetracyanidoborate anion.

Open Access

Cluster Salts [Nb6Cl12(HIm)6]An (with HIm=1H-imidazole and A=Mineral Acid Anion, n=1 or 2) Made in and with Brønsted-basic Ionic Liquids and Liquid Mixtures

  • Pages: 248-254
  • First Published: 03 February 2021
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Ionic liquids and ionic liquid mixtures allow for the preparation of highly crystalline samples of cluster compounds with cationic cluster units. These consist of hexanuclear, octahedral Nb6 cluster cores, edge-bridged by Cl atoms. Each Nb atom carries one 1H-imidazole ligand. Mineral acid anions function as counter anions. In crystals of the title compounds an extensive network of hydrogen bonds exists between the cluster cations, the anions and the co-crystallised solvent molecules.

Open Access

Conductivity and Redox Potentials of Ionic Liquid Trihalogen Monoanions [X3], [XY2], and [BrF4] (X=Cl, Br, I and Y=Cl, Br)

  • Pages: 255-264
  • First Published: 28 January 2021
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The trihalogen monoanions ionic liquids [NEt3Me]+[Cl3]/[Br3]/[I3]/[BrCl2]/[ICl2]/[IBr2] and the tetrafluorobromate(III) monoanion [N2221][BrF4] in acetonitrile were electrochemically analyzed via temperature dependent conductance and cyclic voltammetry measurements. The electrochemical redox potentials were determined of neat salts and in a mixture of pyrrolidinium based ionic liquid, with [Cl3] and [BrF4] being the strongest oxidizing agents.

Communications

Open Access

Planar Iron Hydride Nanoclusters: Combined Spectroscopic and Theoretical Insights into Structures and Building Principles

  • Pages: 265-271
  • First Published: 01 March 2021
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The characterization of discrete metal nanoclusters is challenging due to their rapid growth to larger metal particles. Combined hard X-ray spectroscopy and DFT studies were applied to a series of planar iron clusters which were in full support of their thermodynamically driven formation, the presence of high-spin complexes and bridging hydride ligands. DFT further rationalized a stepwise cluster growth mechanism via formal 2+1 additions of iron hydride species.

Minireviews

Open Access

Metal Sulfide Nanoparticle Synthesis with Ionic Liquids – State of the Art and Future Perspectives

  • Pages: 272-295
  • First Published: 10 March 2021
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Current developments in metal sulfide nanoparticle synthesis using ionic liquids are reviewed. The article focuses on the benefits of using ionic liquids over more traditional approaches. The Minireview also presents the technological challenges associated with the use of ionic liquids to further advance the production and specific property engineering of metal sulfide nanomaterials.

Full Papers

Open Access

Bimetallic Pd/Sn-based Nanoparticles and their Catalytic Properties in the Semihydrogenation of Diphenylacetylene

  • Pages: 296-304
  • First Published: 10 March 2021
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Multimetallic nanoparticles often enhance the catalytic performance of their monometallic counterparts. Here, Pd/Sn-based nanoparticles with intermetallic structure are designed by exploiting the beneficial physico-chemical properties of ionic liquids. Their structure- and composition-dependent catalytic properties in the diphenylacetylene hydrogenation are reported.