Synthesis, crystal structure and properties of μ-tetra-thio-anti-monato-bis-[(cyclam)zinc(II)] perchlorate 0.8-hydrate.

The reaction of Zn(ClO)·6HO with NaSbS·9HO in a water/aceto-nitrile mixture leads to the formation of the title compound, (μ-tetra-thio-anti-monato-κ :')bis-[(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ )zinc(II)] perchlorate 0.8-hydrate, [Zn(SbS)(CHN)]ClO·0.8HO or [(Zn-cyclam)(SbS)][ClO]·0.

Synthesis and in-depth structure determination of a novel metastable high-pressure CrTe phase.

This study reports the synthesis and crystal structure determination of a novel CrTe phase using various experimental and theoretical methods. The average stoichiometry and local phase separation of this quenched high-pressure phase were characterized by synchrotron powder X-ray diffraction and total scattering. Several structural models were obtained using simulated annealing, but all suffered from an imperfect Rietveld refinement, especially at higher diffraction angles.

Sonication-assisted liquid phase exfoliation of two-dimensional CrTe under inert conditions.

Liquid phase exfoliation (LPE) has been used for the successful fabrication of nanosheets from a large number of van der Waals materials. While this allows to study fundamental changes of material properties' associated with reduced dimensions, it also changes the chemistry of many materials due to a significant increase of the effective surface area, often accompanied with enhanced reactivity and accelerated oxidation. To prevent material decomposition, LPE and processing in inert atmosphere have been developed, which enables the preparation of pristine nanomaterials, and to systematically study compositional changes over time for different storage conditions.

Room-Temperature Solid-State Transformation of Na SnS ⋅ 14H O into Na Sn S ⋅ 5H O: An Unusual Epitaxial Reaction Including Bond Formation, Mass Transport, and Ionic Conductivity.

A highly unusual solid-state epitaxy-induced phase transformation of Na SnS  ⋅ 14H O (I) into Na Sn S  ⋅ 5H O (II) occurs at room temperature. Ab initio molecular dynamics (AIMD) simulations indicate an internal acid-base reaction to form [SnS SH] which condensates to [Sn S ] . The reaction involves a complex sequence of O-H bond cleavage, S protonation, Sn-S bond formation and diffusion of various species while preserving the crystal morphology.

Composition-driven archetype dynamics in polyoxovanadates.

Molecular metal oxides often adopt common structural frameworks ( archetypes), many of them boasting impressive structural robustness and stability. However, the ability to adapt and to undergo transformations between different structural archetypes is a desirable material design feature offering applicability in different environments. Using systems thinking approach that integrates synthetic, analytical and computational techniques, we explore the transformations governing the chemistry of polyoxovanadates (POVs) constructed of arsenate and vanadate building units.

Directed Dehydration as Synthetic Tool for Generation of a New Na SnS Polymorph: Crystal Structure, Na Conductivity, and Influence of Sb-Substitution.

We present the convenient synthesis and characterization of the new ternary thiostannate Na SnS (space group ) by directed removal of crystal water molecules from Na SnS ⋅14 H O. The compound represents a new kinetically stable polymorph of Na SnS , which is transformed into the known, thermodynamically stable form (space group ) at elevated temperatures. Thermal co-decomposition of mixtures with Na SbS ⋅9 H O generates solid solution products Na Sn Sb S (x=0.

Crystal structure of μ-tetra-thio-anti-monato-tris[(cyclam)zinc(II)] tetra-thio-anti-monate aceto-nitrile disolvate dihydrate showing Zn disorder over the cyclam ring planes (cyclam = 1,4,8,11-tetra-aza-cyclo-tetra-deca-ne).

Reaction of Zn(ClO)·6HO with cyclam (cyclam = 1,4,8,11-tetra-aza-cyclo-tetra-decane, CHN) and NaSbS in an aceto-nitrile/water mixture led to the formation of crystals of the title compound, [Zn(SbS)(CHN)](SbS)·2CHCN·2HO or [(Zn-cyclam)(SbS)](HO)(aceto-nitrile). The set-up of the crystal structure is similar to that of [(Zn-cyclam)(SbS)]8HO reported recently [Danker (2021 ▸). .

Synthesis and crystal structure of poly[[di-μ-tetra-thio-anti-monato-tris-[(cyclam)cobalt(II)]] aceto-nitrile disolvate dihydrate] (cyclam = 1,4,8,11-tetra-aza-cyclo-tetra-deca-ne).

Reaction of Co(ClO)·6HO with cyclam (cyclam = 1,4,8,11-tetra-aza-cyclo-tetra-deca-ne) and NaSbS·9HO (Schlippesches salt) in a mixture of aceto-nitrile and water leads to the formation of crystals of the title compound with the composition {[Co(SbS)(CHN)]·2CHCN·2HO} or {[(Co-cyclam)(SbS)]·2(aceto-nitrile)·2HO} . The crystal structure of the title compound consists of three crystallographically independent [Co-cyclam] cations, which are located on centers of inversion, one [SbS] anion, one water and one aceto-nitrile mol-ecule that occupy general positions. The aceto-nitrile mol-ecule is disordered over two orientations and was refined using a split model.

Time-dependent investigation of a mechanochemical synthesis of bismuth telluride-based materials and their structural and thermoelectric properties.

Here, we report on the time dependence of a synthesis procedure for generation of both n- and p-type bismuth telluride-based materials. To initiate the reaction, the starting materials were first mechanical pre-reacted. The Rietveld refinements of X-ray diffraction (XRD) data collected after different milling times demonstrate that BiTe was formed after only 10 min, and longer milling times do not alter the composition.

Understanding sodium storage properties of ultra-small FeS nanoparticles - a combined XRD, PDF, XAS and electrokinetic study.

Various electrode materials are considered for sodium-ion batteries (SIBs) and one important prerequisite for developments of SIBs is a detailed understanding about charge storage mechanisms. Herein, we present a rigorous study about Na storage properties of ultra-small FeS nanoparticles, synthesized applying a solvothermal route, which exhibit a very good electrochemical performance as anode material for SIBs. A closer look into electrochemical reaction pathways on the nanoscale, utilizing synchrotron-based X-ray diffraction and X-ray absorption techniques, reveals a complicated conversion mechanism.

Synthesis and crystal structure of bis-[μ-,-bis-(2-amino-eth-yl)ethane-1,2-di-amine]-bis-[,-bis-(2-amino-eth-yl)ethane-1,2-di-amine]-μ-oxido-hexa-μ-oxido-octa-μ-oxido-tetra-oxido-tetra-nickel(II)hexa-tantalum(V) nona-deca-hydrate.

Reaction of K{TaO}·16HO with [Ni(tren)(HO)Cl]Cl·HO in different solvents led to the formation of single crystals of the title compound, [NiTaO(CHN)]·19HO or {[Ni(κ-tren)(μ-κ-tren)]TaO}·19HO (tren is ,-bis-(2-amino-eth-yl)-1,2-ethanediamine, CHN). In its crystal structure, one Lindqvist-type anion {TaO} (point group symmetry ) is connected to two Ni cations, with both of them coordinated by one tren ligand into discrete units. Both Ni cations are sixfold coordinated by O atoms of the anion and N atoms of the organic ligand, resulting in slightly distorted [NiON] octa-hedra for one and [NiON] octa-hedra for the other cation.

The cation and anion bonding modes make a difference: an unprecedented layered structure and a tri(hetero)nuclear moiety in thioantimonates(V).

Mixing solutions of M (M = Cu or Zn) salts containing cyclam (cyclam = 1,4,8,11-tetraazacyclotetradecane) as the ligand and an aqueous solution of NaSbS·9HO at room temperature led to the crystallization of two new compounds within minutes: {[Cu(cyclam)][SbS]}·20HO (I) and {[Zn(cyclam)][SbS]}·8HO (II). In the structure of I [SbS] anions acting as a tridentate ligand join CuNS octahedra generating twelve-membered rings by corner-sharing of SbS and CuNS units. The rings are condensed into layers, which are stacked onto each other in a 6R polytype manner.

Synthetically Produced Isocubanite as an Anode Material for Sodium-Ion Batteries: Understanding the Reaction Mechanism During Sodium Uptake and Release.

Bulk isocubanite (CuFeS) was synthesized via a multistep high-temperature synthesis and was investigated as an anode material for sodium-ion batteries. CuFeS exhibits an excellent electrochemical performance with a capacity retention of 422 mA h g for more than 1000 cycles at a current rate of 0.5 A g (0.

Long-Term Stable, High-Capacity Anode Material for Sodium-Ion Batteries: Taking a Closer Look at CrPS from an Electrochemical and Mechanistic Point of View.

Electrochemical performance of the layered compound CrPS for the usage as anode material in sodium-ion batteries (SIBs) was examined and exceptional reversible long-term capacity and capacity retention were found. After 300 cycles, an extraordinary reversible capacity of 687 mAh g at a current rate of 1 A g was achieved, while rate capability tests showed an excellent capacity retention of 100%. Detailed evaluation of the data evidence a change of the electrochemical reaction upon cycling leading to the striking long-term performance.

Superior Sodium Storage Properties in the Anode Material NiCr S for Sodium-Ion Batteries: An X-ray Diffraction, Pair Distribution Function, and X-ray Absorption Study Reveals a Conversion Mechanism via Nickel Extrusion.

The pseudo-layered sulfide NiCr S exhibits outstanding electrochemical performance as anode material in sodium-ion batteries (SIBs). The Na storage mechanism is investigated by synchrotron-based X-ray scattering and absorption techniques as well as by electrochemical measurements. A very high reversible capacity in the 500th cycle of 489 mAh g is observed at 2.

Three intersecting {V} rings: {VSb}, an ultra-large polyoxovanadate cluster shell.

[VIV30SbIII8O78]12-, currently the largest known antimonato-polyoxovanadate (Sb-POV), features three perpendicular, intersecting 12-membered rings of edge-sharing O4V[double bond, length as m-dash]O square pyramids. While in two rings the apices of all O4V[double bond, length as m-dash]O pyramids point outwards, four apices of the third ring are directed into the cavity of the cluster shell, a concave structural motif not previously observed in polyoxovanadate chemistry. SbIII centers cap the eight niches defined by the octands of the {V30O78} cluster shell, resulting in discrete trigonal pyramidal SbO3 units, a second unprecedented feature.

CuFeS as a Very Stable High-Capacity Anode Material for Sodium-Ion Batteries: A Multimethod Approach for Elucidation of the Complex Reaction Mechanisms during Discharge and Charge Processes.

Highly crystalline CuFeS containing earth-abundant and environmentally friendly elements prepared via a high-temperature synthesis exhibits an excellent electrochemical performance as an anode material in sodium-ion batteries. The initial specific capacity of 460 mAh g increases to 512 mAh g in the 150th cycle and then decreases to a still very high value of 444 mAh g at 0.5 A g in the remaining 550 cycles.

Mechanochemical Synthesis and Magnetic Characterization of Nanosized Cubic Spinel FeCrS Particles.

Nanosized samples of the cubic thiospinel FeCrS were synthesized by ball milling of FeS and CrS precursors followed by a distinct temperature treatment between 500 and 800 °C. Depending on the applied temperature, volume weighted mean ( ) particle sizes of 56 nm (500 °C), 86 nm (600 °C), and 123 nm (800 °C) were obtained. All samples show a transition into the ferrimagnetic state at a Curie temperature of ∼ 167 K only slightly depending on the annealing temperature.

Synthesis and crystal structure of (1,4,7,10-tetra-aza-cyclo-dodecane-κ )(tetra-sulfido-κ , )manganese(II).

The title compound, [Mn(S)(CHN)], was accidentally obtained by the hydro-thermal reaction of Mn(ClO)·6HO, cyclen (cyclen = 1,4,7,10-tetra-aza-cyclo-dodeca-ne) and NaSbS·9HO in water at 413 K, indicating that polysulfide anions might represent inter-mediates in the synthesis of thio-metallate compounds using NaSbS·9HO as a reactant. X-ray powder diffraction proves that the sample is slightly contaminated with NaSb(OH) and an unknown crystalline phase. The crystal investigated was twinned with a twofold rotation axis as the twin element, and therefore a twin refinement using data in HKLF-5 format was performed.

Synthesis and crystal structure of -poly[[bis[(2,2';6',2''-terpyridine)-manganese(II)]-μ-penta-thio-dianti-monato] tetra-hydrate] showing a 1D MnSbS network.

The asymmetric unit of the title compound, {[MnSbS(CHN)]·4HO} , consists of two crystallographically independent Mn ions, two unique terpyridine ligands, one [SbS] anion and four solvent water mol-ecules, all of which are located in general positions. The [SbS] anion consists of two SbS units that share common corners. Each of the Mn ions is fivefold coordinated by two symmetry-related S atoms of [SbS] anions and three N atoms of a terpyridine ligand within an irregular coordination.

HfTe: Enhancing Magnetoresistance Properties by Improvement of the Crystal Growth Method.

We present a systematic study on the magnetotransport properties of HfTe single crystals grown by different synthetic protocols. Both chemical vapor transport (CVT) as well as the self-flux method were applied. Depending on the synthetic procedure the crystal quality is reflected by the residual resistivity ratio (RRR).

Unveiling the Reaction Mechanism during Li Uptake and Release of Nanosized "NiFeMnO": Operando X-ray Absorption, X-ray Diffraction, and Pair Distribution Function Investigations.

Here, we report that the trimetallic nanosized oxide NiFeMnO consists of a mixture of NiO and a strained cubic spinel phase, which is clearly demonstrated by analysis of the pair distribution function (PDF) and synchrotron X-ray data. Such a finding can easily be overlooked by using only inhouse X-ray powder diffraction, leading to inaccurate assumption of the stoichiometry and oxidation states. Such advanced characterization is essential because a homogeneous distribution of the elements is observed in energy-dispersive X-ray spectroscopy maps, giving no hints for a phase separation.

Synthesis, Crystal Structure, and Selected Properties of [Au(S CNH ) ]SCN: A Precursor for Gold Macro-Needles Consisting of Gold Nanoparticles Glued by Graphitic Carbon Nitride.

A new preparation route is developed for the synthesis of needle-like crystals of [Au(S CNH ) ]SCN, which avoids disproportionation of the Au salt used as a starting material. In the crystal structure, the two crystallographically independent Au centers are in a square-planar environment of two S CNH ligands. The Hirshfeld surface analysis reveals the presence of noncovalent intermolecular S⋅⋅⋅S interactions, which are essential for the spatial arrangement of the molecules.

Synthesis and Characterization of a Rare Transition-Metal Oxothiostannate and Investigation of Its Photocatalytic Properties.

The new transition-metal oxothiostannate [Ni(cyclen)(HO)][SnSO]·∼13HO (1) was prepared under hydrothermal conditions using NaSnS·14HO as the precursor in the presence of [Ni(cyclen)(HO)](ClO)·HO. Compound 1 comprises the [SnSO] anion constructed by the T3-type supertetrahedron [SnS] and the [SnO] anti-T2 cluster. Channels host the HO molecules, and the sample can be reversibly dehydrated and rehydrated without significantly affecting the crystallinity of the material.

Nanostructured tungsten sulfides: insights into precursor decomposition and the microstructure using X-ray scattering methods.

Herein we present an in-depth study of precursor derived tungsten sulfides, with a focus on their micro- and local structures. We prepared a new tetrathiotungstate based precursor (N2H5)2WS4 and unveiled the details of its unique decomposition mechanism by a combination of in situ and ex situ analytical techniques. Upon heating the precursor, a new compound with composition (NH4)(N2H5)WS4 is formed by the decomposition of one hydrazinium molecule.