Pressure-Induced Dislocations and Their Influence on Ionic Transport in Li+-Conducting Argyrodites.

The influence of the microstructure on the ionic conductivity and cell performance is a topic of broad scientific interest in solid-state batteries. The current understanding is that interfacial decomposition reactions during cycling induce local strain at the interfaces between solid electrolytes and the anode/cathode, as well as within the electrode composites. Characterizing the effects of internal strain on ion transport is particularly important, given the significant local chemomechanical effects caused by volumetric changes of the active materials during cycling. Here, we show the effects of internal strain on the bulk ionic transport of the argyrodite Li6PS5Br. Internal strain is reproducibly induced by applying pressures with values up to 10 GPa. An internal permanent strain is observed in the material, indicating long-range strain fields typical for dislocations. With increasing dislocation densities, an increase in the lithium ionic conductivity can be observed that extends into improved ionic transport in solid-state battery electrode composites. This work shows the potential of strain engineering as an additional approach for tuning ion conductors without changing the composition of the material itself.

Pressure-Assisted Synthesis of Highly Crystalline 1T''-Lix MoS2.

Lix MoS2 is not only a lithium battery material, but is also an important precursor for the synthesis of MoS2 nanomaterials. Current syntheses of MoS2 , such as in n-butyllithium/LiBH4 or electrochemically, are not satisfying in terms of defined stoichiometry and crystallinity, so an accurate experimental crystal structure determination of this important and widely used material has been long awaited. A high-pressure/high-temperature synthesis yielded highly crystalline 1T''-Lix MoS2 (x=1, 1.333). 1T''-LiMoS2 crystallizes in the space group P 1 ‾ $\bar 1$ with a=6.2482(3) Å, b=6.6336(3) Å, c=6.7480(3) Å, α=119.321(2)°, ß=90.010(2)° and γ=90.077(2)°. The arrangement of Mo atoms within the b-c-plane confirmed a predicted Peierls distortion. A similar atom distribution pattern to that of Mo is also observed for the lithium atoms. Calculation of bond valence site energies gave an activation barrier of 1.244 eV for 2D lithium-ion migration. For x=1.333, a phase-pure synthesis was achieved.

A Comparative Study of a High-Pressure Polymorph of I2O5 and its Ambient-Pressure Modification.

A hitherto unknown modification of I2O5 was obtained from high-pressure/high-temperature syntheses in a Walker-type multianvil device at 8 GPa and 250 °C. HP-I2O5 crystallizes in the monoclinic crystal system with space group P21/c (no. 14) with the unit cell parameters a=12.0612(3) Å, b=4.8613(2) Å, c=6.9585(2) Å, ß=100.10(1)° (at 173 K), and four formula units per cell. The single-crystal structure data are accompanied by powder X-ray diffraction data at ambient and elevated temperatures. Furthermore, DFT calculations were carried out to investigate the phase transition between the ambient-pressure polymorph NP-I2O5 to the newly synthesized high-pressure phase.

High-Pressure and High-Temperature Dion-Jacobson Layered Perovskite Polymorphs of KWO3 F.

Two new Dion-Jacobson layered perovskite polymorphs of the known oxyfluoride compound KWO3 F are reported. A high-pressure modification was synthesized using a multianvil setup and subsequently transformed into a high-temperature phase at ∼311 °C. The crystal structures of both polymorphs were determined by use of single-crystal X-ray diffraction and are described in detail herein. Differential thermal analyses and thermogravimetric analyses were carried out to further investigate the phase transition characteristics. Bond valence (BV) and charge distribution (CHARDI) calculations confirm the occupancy of mixed O|F anion positions, and Rietveld refinements as well as MAPLE calculations support the structure models.

Li2 Ba4 Al2 Ta2 N8 O, the First Barium Nitridoalumotantalate with BCT-Zeolite Type Structure.

Single-crystals of Li2 Ba4 Al2 Ta2 N8 O:Eu2+ were synthesized from Ba3 N2 , Al2 O3 , Li3 N, Eu2 O3 , and lithium metal by a high-temperature solid-state reaction in a weld shut tantalum ampule. The crystal structure of Li2 Ba4 Al2 Ta2 N8 O was determined by single-crystal X-ray diffraction and it crystallizes in the orthorhombic space group Pnnm (no. 58) with the lattice parameters a=1006.71(3), b=1026.58(3), c=607.10(2) pm, and a volume of V=0.62742(3) nm3 . The compound is built up from AlN4 and TaN4 tetrahedra, which form a three-dimensional network corresponding to the BCT-zeolite type structure. Li2 Ba4 Al2 Ta2 N8 O is homeotypic to Li2 Sr4 Si4 N8 O and Li2 Sr4 Al2 Ta2 N8 O but, additionally, it could be successfully doped with the activator ion Eu2+ and hence features an experimental observed overall emission at λmax =565 nm (fwhm=89 nm) consisting of a superposition of two adjusted emission bands at λmax =557 nm (fwhm=69 nm) and at λmax =604 nm (fwhm=102 nm).

Ba4Al7Li28.08O26.92N1.08, the Barium Oxonitridolithoaluminate with a Highly Condensed LiO4 Tetrahedra Framework.

The new compound Ba4Al7Li28.08O26.92N1.08 consists of AlO4/AlO3N tetrahedra, 10-fold coordinated Ba2+ cations, and a highly condensed edge- and corner-sharing LiO4 tetrahedra framework, which leads to a degree of condensation greater than 1. The first barium oxonitridolithoaluminate was synthesized by a high-temperature solid-state reaction in a weld-shut tantalum ampoule and the crystal structure has been determined by single-crystal X-ray diffraction. Ba4Al7Li28.08O26.92N1.08 crystallizes in the monoclinic space group P21/m (no. 11) with the lattice parameters a = 1052.41(3), b = 615.93(2), c = 1088.45(4) pm, ß = 98.86(1)°, and a volume of V = 0.69712(4) nm3. In addition, Ba4Al7Li28.08O26.92N1.08 doped with the activator ion Eu2+, exhibits a broad band emission with a maximum at λmax = 524 nm (2.34 eV) with a fwhm of 112 nm (4373 cm-1/0.54 eV), which can be described by a superposition of two adjusted emission bands at λmax = 515 nm (2.41 eV) with a fwhm of 70 nm (2704 cm-1/0.34 eV), and at λmax = 574 nm (2.18 eV) with a fwhm of 127 nm (4127 cm-1/0.51 eV).

Photoluminescence of Mn2+ in the Borosulfate Zn[B2 (SO4 )4 ] : Mn2+ -A Tool to Detect Weak Coordination Behavior of Ligands.

The impact of the surrounding ligand field is successfully exploited in the case of Eu2+ to tune the emission characteristics of inorganic photoactive materials with potential application in, e.g., phosphor-converted white light-emitting diodes (pc-wLEDs). However, the photoluminescence of Mn2+ related to intraconfigurational 3d5 -3d5 transitions is also strongly dependent on local ligand field effects and has been underestimated in this regard so far. In this work, we want to revive the idea how to electronically tune the emission color of a transition metal ion in inorganic hosts by unusual electronic effects in the metal-ligand bond. The concept is explicitly demonstrated for the weakly coordinating layer-like borosulfate ligand in the Mn2+ -containing solid solutions Zn1-x Mnx [B2 (SO4 )4 ] (x = 0, 0.03, 0.04, 0.05, 0.10). Zn[B2 (SO4 )4 ]:Mn2+ shows orange narrow-band luminescence at 590 nm, which is an unusually short wavelength for octahedrally coordinated Mn2+ and indicates an uncommonly weak ligand field. On the other hand, the analysis of the interelectronic Racah repulsion parameters reveals ionic Mn-O bonds with values close to the Racah parameters of the free Mn2+ ion. Overall, this strategy demonstrates that electronic control of the metal-ligand bond can be a tool to make Mn2+ a potent alternative emitter to Eu2+ for inorganic phosphors.

Fundamental Study of the Optical and Vibrational Properties of Fx-AZB@MOF systems as Functions of Dye Substitution and the Loading Amount.

Controlling the switching efficiency of photoactive hybrid systems is an obligatory key prerequisite for systematically improving the design of functional materials. By modulating the degree of fluorination and the amount being embedded into porous hosts, the E/Z ratios of fluorinated azobenzenes were adjusted as both functions of substitution and the degree of loading. Octafluoroazobenzene (F8-AZB) and perfluoroazobenzene (F10-AZB) were inserted into porous DMOF-1. Especially for perfluoroazobenzene (F10-AZB), an immense stabilization of the E isomer was observed. In complementary molecular dynamics simulations performed at the DFTB (density functional tight binding) level, an in-depth characterization of the interactions of the different photoisomers and the host structure was carried out. On the basis of the resulting structural and energetic data, the experimentally observed increase in the amount of the Z conformer for F8-AZB can be explained, while the stabilization of E-F10-AZB can be directly related to a fundamentally different interaction motif compared to its tetra- and octafluorinated counterparts.

On the Reduction of MoO3 to MoO2 : A Path to Control the Particle Size and Morphology.

During the reduction of molybdenum trioxide (MoO3 ) to metallic molybdenum, the first reduction step yielding molybdenum dioxide as an intermediary product is of crucial importance. In this study, we examined the impact of the parameters reduction temperature, water influx, and potassium content on the hydrogen reduction of this first reaction step. Beginning from the same starting material, the chemical vapor transport mechanism was utilized to yield the phase pure MoO2 . Analyses including powder X-ray diffraction, inductively coupled plasma-mass spectrometry, scanning electron microscopy, and high performance optical microscopy were performed on the product phases. Modulations of the specific surface areas of molybdenum dioxide ranging from 2.28 to 0.41 m2 /g were possible. Furthermore, a distinct shift from small plate-like grains to cuboid-like forms was achieved.

Rb[Li5 Si2 O7 ] - A Latecomer in the Family of Alkali Lithosilicates Hiding a Green-Emitting Lithosilicate.

In order to expand the field of alkali lithosilicates, a new representative of the substance class with a previously unknown structure type was found based on solid-state synthesis. The novel compound with the sum formula Rb[Li5 Si2 O7 ] crystallizes in the orthorhombic space group Pbcm (no. 57) with a=7.6269(3), b=9.5415(4), and c=9.4095(3) Šby means of single-crystal X-ray diffraction. The structure consists of a highly condensed lithosilicate framework, built up of corner- and edge-linked [LiO4 ]-tetrahedra and [Si2 O7 ]-units, and the rubidium ions aligned in channels. Suitable crystals of the material were obtained using sealed tantalum ampoules as reaction tube at a temperature of 750 °C. The new compound was further characterized via powder diffraction, Rietveld analysis, and EDX measurements. At first glance, Eu2+ -doped Rb[Li5 Si2 O7 ] reveals an intense green luminescence. In-depth crystal analysis shows that a core-shell formation is present even for apparently high quality single-crystals. As a minority phase, the known green phosphor RbLi[Li3 SiO4 ]2 :Eu2+ is the origin of the luminescence, representing a tiny core inside of the particles surrounded by a large matrix of transparent Rb[Li5 Si2 O7 ] dominating the single-crystal diffraction pattern.

Polymorphs of the Gadolinite-Type Borates ZrB2 O5 and HfB2 O5 Under Extreme Pressure.

Based on the results from previous high-pressure experiments on the gadolinite-type mineral datolite, CaBSiO4 (OH), the behavior of the isostructural borates ß-HfB2 O5 and ß-ZrB2 O5 have been studied by synchrotron-based in situ high-pressure single-crystal X-ray diffraction experiments. On compression to 120 GPa, both borate layer-structures are preserved. Additionally, at ≈114 GPa, the formation of a second phase can be observed in both compounds. The new high-pressure modification γ-ZrB2 O5 features a rearrangement of the corner-sharing BO4 tetrahedra, while still maintaining the four- and eight-membered rings. The new phase γ-HfB2 O5 contains ten-membered rings including the rare structural motif of edge-sharing BO4 tetrahedra with exceptionally short B-O and B⋅⋅⋅B distances. For both structures, unusually high coordination numbers are found for the transition metal cations, with ninefold coordinated Hf4+ , and tenfold coordinated Zr4+ , respectively. These findings remarkably show the potential of cold compression as a low-energy pathway to discover metastable structures that exhibit new coordinations and structural motifs.

Coexistence of Two Different Distorted Octahedral [MnF6 ]3- Sites in K3 [MnF6 ]: Manifestation in Spectroscopy and Magnetism.

As a consequence of the static Jahn-Teller effect of the 5 E ground state of MnIII in cubic structures with octahedral parent geometries, their octahedral coordination spheres become distorted. In the case of six fluorido ligands, [MnF6 ]3- anions with two longer and four shorter Mn-F bonds making elongated octahedra are usually observed. Herein, we report the synthesis of the compound K3 [MnF6 ] through a high-temperature approach and its crystallization by a high-pressure/high-temperature route. The main structural motifs are two quasi-isolated, octahedron-like [MnF6 ]3- anions of quite different nature compared to that met in ideal octahedral MnIII Jahn-Teller systems. Owing to the internal electric field of Ci symmetry dominated by the next-neighbour K+ ions acting on the MnIII sites, both sites, the pseudo-rhombic (site 1) and the pseudo-tetragonally elongated (site 2) [MnF6 ]3- anions are present in K3 [MnF6 ]. The compound was characterized by single-crystal and powder X-ray diffraction, and magnetometry as well as by FTIR, Raman, and ligand field spectroscopy. A theoretical interpretation of the electronic structure and molecular geometry of the two Mn sites in the lattice is given by using a vibronic coupling model with parameters adjusted from multireference ab-initio cluster calculations.

Modulating the Optical Characteristics of Spiropyran@Metal-Organic Framework Composites as a Function of Spiropyran Substitution.

Understanding the interactions between the single components of hybrid systems is essential to drive the development of advanced functional materials. A prerequisite for this is the systematic variation of the building blocks of such compounds. Focusing on spiropyran@metal-organic framework (MOF) composite materials with noncovalently attached spiropyran dyes, both the host scaffold and the dye molecules can be systematically tuned. In this work, a broad substitution pattern was applied to systematically elucidate the characteristics of the resulting hybrid materials as a function of the supplemental substitution on spiropyran. The newly developed 12 composites exhibit substitution and host-dependent optical characteristics, which are particularly affected by the substitution of the 6'-position on the chromene ring. Through the favorable combination of the MOF host's polarity and an adequate strength of the spiropyran's indolinedonor-chromeneacceptor pair, reversible conversion between photoisomers is efficiently accomplished, especially for nitro-substituted spiropyrans inside MIL-68(In).

Syntheses and Characterization of the Mixed-Valent Manganese(II/III) Fluorides Mn2F5 and Mn3F8.

We obtained single crystals of the binary mixed-valent fluorides Mn2F5 and Mn3F8 using a high-pressure/high-temperature approach. Mn2F5 crystallizes isotypic to CaCrF5 in the monoclinic space group C2/c (No. 15), with a = 8.7078(8) Å, b = 6.1473(6) Å, c = 7.7817(7) Å, ß = 117.41(1)°, V = 369.80(6) Å3, Z = 4, and mC28 at T = 173 K. Mn3F8 crystallizes in the monoclinic space group P21 (No. 4) with a = 5.5253(2) Å, b = 4.8786(2) Å, c = 9.9124(4) Å, ß = 92.608(2)°, V = 266.92(2) Å3, Z = 2, and mP22 at T = 183 K and presents a new structure type. Crystal-chemical reasoning, CHARDI calculations, and quantum-chemical calculations allowed for the assignment of the oxidation states of the Mn atoms. In both bulk compounds, MnF2 was present as an impurity, as evidenced by powder X-ray diffraction and IR and Raman spectroscopy.

The First High-Pressure Chromium Oxonitridoborate CrB4 O6 N-an Unexpected Link to Nitridosilicate Chemistry.

CrB4 O6 N crystallizes in the non-centrosymmetric space group P63 mc (no. 186) with the lattice parameters a=5.1036(1), c=8.3519(3) Å, and a volume of 188.40(1) Å3 . It was synthesized in a high-pressure/high-temperature experiment at 7 GPa and 1673 K and represents the first high-pressure oxonitridoborate. It is built up of starlike-shaped entities of four BO3 N tetrahedra, connected via one common nitrogen atom that resembles the fourfold-coordinated nitrogen atoms in the homeotypic nitridosilicates MYbSi4 N7 (M=Sr, Ba). Building up a network with channels that contain the Cr3+ ions, CrB4 O6 N contains for the first time a tetrahedral building unit in contrast to trigonal planar B(O/N)3 entities in all other known oxonitridoborates. The structural relations as well as the results of spectroscopic measurements and calculations on the chromium oxonitridoborate are discussed.

Triple-Vertex Linkage of (BO4 )-Tetrahedra in a Borosulfate: Synthesis, Crystal Structure, and Quantum-Chemical Investigation of Sr[B3 O(SO4 )4 (SO4 H)].

Borosulfates are classified as silicate analogue materials. The number of crystallographically characterized compounds is still limited, whereas the structural diversity is already impressive. The anionic substructures of borosulfates exhibit vertex-connected (BO4 )- and (SO4 )-tetrahedra, whereas bridging between two (SO4 )- or even between two (BO4 )-tetrahedra is scarce. The herein presented compound Sr[B3 O(SO4 )4 (SO4 H)] is the first borosulfate with a triple-vertex linkage of three (BO4 ) tetrahedra via one common oxygen atom. DFT calculations complement the experimental studies. Bader charges (calculated for all atoms) as well as charge-density calculations give hint to the electron distribution within the anionic substructure and density-of-states calculations support the interpretation of the bonding situation.

Borosulfates-Synthesis and Structural Chemistry of Silicate Analogue Compounds.

Borosulfates are oxoanionic compounds consisting of condensed sulfur- and boron-centered tetrahedra. Hitherto, they were mostly achieved from solvothermal syntheses in SO3 -enriched sulfuric acid, or from reactions with the superacid H[B(HSO4 )4 ]. The crystal structures are very similar to those of the corresponding class of silicates and their substitution variants, especially regarding the typical structural motif of corner-sharing tetrahedra. However, the borosulfates are supposed to be even more versatile, because (BO3 ) units might also be part of the anionic network. The following article deals with detailed reports on the different synthesis strategies, the crystal chemistry of borosulfates in comparison to silicates, and their hitherto identified properties.

A Double-Band Emitter with Ultranarrow-Band Blue and Narrow-Band Green Luminescence.

Understanding the origin and mechanisms of luminescence is a crucial point when it comes to the development of new phosphors with targeted luminescence properties. Herein, a new phosphor belonging to the substance class of alkali metal lithosilicates with the generalized sum formula Cs4-x-y-z Rbx Nay Liz [Li3 SiO4 ]4 :Eu2+ is reported. Single crystals of the cyan-emitting UCr4 C4 -type phosphor show a peculiar double-band luminescence with one ultranarrow emission band at 473 nm and a narrow emission band at 531 nm under excitation with UV light (λexc =408 nm). Regarding occupation of the channels by the light metal ions, investigations of single-crystal XRD data led to the assumption that domain formation with distinct lithium- and sodium-filled channels occurs. Depending on which of these channels hosts the activator ion Eu2+ , a green or blue emission results. The herein-presented results shed new light on the luminescence process in the well-studied UCr4 C4 -type alkali metal lithosilicate phosphors.

Ni[B2 (SO4 )4 ] and Co[B2 (SO4 )4 ]: Unveiling Systematic Trends in Phyllosilicate Analogue Borosulfates.

Borosulfates are compounds analogous to silicates, with heteropolyanionic subunits of vertex-linked (SO4 )- and (BO4 )-tetrahedra. In contrast to the immense structural diversity of silicates, the number of borosulfates is yet very limited and the extent of their properties is still unknown. This is particularly true for representatives with phyllosilicate and tectosilicate analogue anionic substructures. Herein, we present Ni[B2 (SO4 )4 ] and Co[B2 (SO4 )4 ], two new borosulfates with phyllosilicate analogue topology. While the anionic subunits of both structures are homeotypic, the positions of the charge compensating cations differ significantly: NiII is located between the borosulfate layers, while CoII -in contrast-is embedded within the layer. Detailed analysis of these two structures based on single-crystal X-ray diffraction, magnetochemical investigations, X-ray photoelectron spectroscopy, and quantum chemical calculations, unveiled the reasons for this finding. By in silico comparison with other divalent borosulfates, we uncovered systematic trends for phyllosilicate analogues leading to the prediction of new species.

La3 B6 O13 (OH): The First Acentric High-Pressure Borate Displaying Edge-Sharing BO4 Tetrahedra.

La3 B6 O13 (OH) was obtained by a high-pressure/high-temperature experiment at 6 GPa and 1673 K. The compound crystallizes in the space group P21 (no. 4) with the lattice parameters a=4.785(2), b=12.880(4), c=7.433(3) Å, and ß=90.36(10)°, and is built up of corner- as well as edge-sharing BO4 tetrahedra. It represents the first acentric high-pressure borate containing these B2 O6 entities. The compound develops borate layers of "sechser"-rings with the La3+ cations positioned between the layers. Single-crystal and powder X-ray diffraction, vibrational and MAS NMR spectroscopy, second-harmonic generation (SHG) and thermoanalytical measurements, as well as computational methods were used to affirm the proposed structure and the B2 O6 entities.