Synthesis and Characterization of 5‐Cyanotetrazolide‐Based Ionic Liquids

New salts based on imidazolium, pyrrolidinium, phosphonium, guanidinium, and ammonium cations together with the 5‐cyanotetrazolide anion [C₂N₅]^? are reported. Depending on the nature of cation–anion interactions, characterized by XRD, the ionic liquids (ILs) have a low viscosity and are liquid at room temperature or have higher melting temperatures. Thermogravimetric analysis, cyclic voltammetry, viscosimetry, and impedance spectroscopy display a thermal stability up to 230 °C, an electrochemical window of 4.5 V, a viscosity of 25 mPa s at 20 °C, and an ionic conductivity of 5.4 mS cm^?1 at 20 °C for the IL 1‐butyl‐1‐methylpyrrolidinium 5‐cyanotetrazolide [BMPyr][C₂N₅]. On the basis of these results, the synthesized compounds are promising electrolytes for lithium‐ion batteries.     

Layered Black Phosphorus: Strongly Anisotropic Magnetic,Electronic, and Electron‐Transfer Properties

Layered elemental materials, such as black phosphorus, exhibit unique properties originating from their highly anisotropic layered structure. The results presented herein demonstrate an anomalous anisotropy for the electrical, magnetic, and electrochemical properties of black phosphorus. It is shown that heterogeneous electron transfer from black phosphorus to outer‐ and inner‐sphere molecular probes is highly anisotropic. The electron‐transfer rates differ at the basal and edge planes. These unusual properties were interpreted by means of calculations, manifesting the metallic character of the edge planes as compared to the semiconducting properties of the basal plane. This indicates that black phosphorus belongs to a group of materials known as topological insulators. Consequently, these effects render the magnetic properties highly anisotropic, as both diamagnetic and paramagnetic behavior can be observed depending on the orientation in the magnetic field.     

A Thioxanthone Sensitizer with a Chiral Phosphoric Acid Binding Site: Properties and Applications in Visible Light-Mediated Cycloadditions

A chiral phosphoric acid with a 2,2’-binaphthol core was prepared that displays two thioxanthone moieties at the 3,3’-position as light-harvesting antennas. Despite its relatively low triplet energy, the phosphoric acid was found to be an efficient catalyst for the enantioselective intermolecular [2+2] photocycloaddition of β-carboxyl-substituted cyclic enones (e.r. up to 93:7). Binding of the carboxylic acid to the sensitizer is suggested by NMR studies and by DFT calculations to occur by means of two hydrogen bonds. The binding event not only enables an enantioface differentiation but also modulates the triplet energy of the substrates.     

Enantiotopos‐Selective CH Oxygenation Catalyzed by a Supramolecular Ruthenium Complex

Spirocyclic oxindoles undergo an enantioselective oxygenation reaction (nine examples; e.r. up to 97:3) upon catalysis by a chiral ruthenium porphyrin complex (1 mol %). The catalyst exhibits a lactam ring, which is responsible for substrate association through hydrogen bonds, and an active ruthenium center, which is in a defined spatial relationship to the oxygenation substrate. DFT calculations illustrate the perfect alignment of the active site with the reactive C? H bond and suggest—in line with the kinetic isotope effect—an oxygen rebound mechanism for the reaction.     

Li17Sb13S28: A New Lithium Ion Conductor and addition to the Phase Diagram Li2S–Sb2S3

Li₁₇Sb₁₃S₂₈ was synthesized by solid‐state reaction of stoichiometric amounts of anhydrous Li₂S and Sb₂S₃. The crystal structure of Li₁₇Sb₁₃S₂₈ was determined from dark‐red single crystals at room temperature. The title compound crystallizes in the monoclinic space group C2/m (no. 12) with a=12.765(2) Å, b=11.6195(8) Å, c=9.2564(9) Å, β=119.665(6)°, V=1193.0(2) ų, and Z=4 (data at 20 °C, lattice constants from powder diffraction). The crystal structure contains one cation site with a mixed occupation by Li and Sb, and one with an antimony split position. Antimony and sulfur form slightly distorted tetragonal bipyramidal [SbS₅E] units (E=free electron pair). Six of these units are arranged around a vacancy in the anion substructure. The lone electron pairs E of the antimony(III) cations are arranged around these vacancies. Thus, a variant of the rock salt structure type with ordered vacancies in the anionic substructure results. Impedance spectroscopic measurements of Li₁₇Sb₁₃S₂₈ show a specific conductivity of 2.9×10^?9 Ω^?1 cm^?1 at 323 K and of 7.9×10^?6 Ω^?1 cm^?1 at 563 K, the corresponding activation energy is E_A=0.4 eV below 403 K and E_A=0.6 eV above. Raman spectra are dominated by the Sb?S stretching modes of the [SbS₅] units at 315 and 341 cm^?1 at room temperature. Differential thermal analysis (DTA) measurements of Li₁₇Sb₁₃S₂₈ indicate peritectic melting at 854 K.     

Strong,Thermally Superinsulating Biopolymer–Silica Aerogel Hybrids by Cogelation of Silicic Acid with Pectin

Silica aerogels are excellent thermal insulators, but their brittle nature has prevented widespread application. To overcome these mechanical limitations, silica–biopolymer hybrids are a promising alternative. A one‐pot process to monolithic, superinsulating pectin–silica hybrid aerogels is presented. Their structural and physical properties can be tuned by adjusting the gelation pH and pectin concentration. Hybrid aerogels made at pH 1.5 exhibit minimal dust release and vastly improved mechanical properties while remaining excellent thermal insulators. The change in the mechanical properties is directly linked to the observed “neck‐free” nanoscale network structure with thicker struts. Such a design is superior to “neck‐limited”, classical inorganic aerogels. This new class of materials opens up new perspectives for novel silica–biopolymer nanocomposite aerogels.     

Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in [(Cp*Mo)2(μ,η6:η6‐P6)] Towards the “Naked” Cations Cu+, Ag+, and Tl+

Although the cyclo‐P₆ complex [(Cp*Mo)₂(μ,η⁶:η⁶‐P₆)] ( 1 ) was reported 30 years ago, little is known about its chemistry. Herein, we report a high‐yielding synthesis of 1 , the complex 2 , which contains an unprecedented cyclo‐P₁₀ ligand, and the reactivity of 1 towards the “naked” cations Cu⁺, Ag⁺, and Tl⁺. Besides the formation of the single oxidation products 3 a,b which have a bisallylic distorted cyclo‐P₆ middle deck, the [M( 1 )₂]⁺ complexes are described which show distorted square‐planar (M=Cu( 4 a ), Ag( 4 b )) or distorted tetrahedral coordinated (M=Cu( 5 )) M⁺ cations. The choice of solvent enabled control over the reaction outcome for Cu⁺, as proved by powder XRD and supported by DFT calculations. The reaction with Tl⁺ affords a layered two‐dimensional coordination network in the solid state.