The Non-Centrosymmetric Borate Hydride SrBa(BO)H.

SrBa(BO)H, as the second compound to combine borate and hydride ions, has been synthesized by a mechanochemical synthesis route. The structure has been elucidated by synchrotron X-ray and neutron diffraction and determined to crystallize in the non-centrosymmetric space group P6mc (186) with the cell parameters a=10.87762(15) Å and c=6.

Chemical Bonding and Crystal Structure Schemes in Atomic/Molecular Layer Deposited Fe-Terephthalate Thin Films.

Advanced deposition routes are vital for the growth of functional metal-organic thin films. The gas-phase atomic/molecular layer deposition (ALD/MLD) technique provides solvent-free and uniform nanoscale thin films with unprecedented thickness control and allows straightforward device integration. Most excitingly, the ALD/MLD technique can enable the in situ growth of novel crystalline metal-organic materials.

Bismuth as a Z-Type Ligand: an Unsupported Pt-Bi Donor-Acceptor Interaction and its Umpolung by Reaction with H.

Establishing unprecedented types of bonding interactions is one of the fundamental challenges in synthetic chemistry, paving the way to new (electronic) structures, physicochemical properties, and reactivity. In this context, unsupported element-element interactions are particularly noteworthy since they offer pristine scientific information about the newly identified structural motif. Here we report the synthesis, isolation, and full characterization of the heterobimetallic Bi/Pt compound [Pt(PCy)(BiMe)(SbF)] (1), bearing the first unsupported transition metal→bismuth donor/acceptor interaction as its key structural motif.

Visualizing Noncovalent Interactions and Property Prediction of Submicron-Sized Charge-Transfer Crystals from ab-initio Determined Structures.

The charge-transfer (CT) interactions between organic compounds are reflected in the (opto)electronic properties. Determining and visualizing crystal structures of CT complexes are essential for the design of functional materials with desirable properties. Complexes of pyranine (PYR), methyl viologen (MV), and their derivatives are the most studied water-based CT complexes.

Centrosymmetric to non-centrosymmetric transition in the CaMnTiO double perovskite system studied through structural analysis and dielectric properties.

We have used high-pressure synthesis to synthesize samples of CaMnTiO double perovskite, where varies between 0.2 and 1. The synthesized materials were structurally characterized with powder X-ray diffraction (XRD).

[BrF] - a unique molecular tetrahedral interhalogen ion containing a μ-bridging fluorine atom surrounded by BrF molecules.

The reaction of [NMe][BrF] with an excess of BrF leads to the compound [NMe][BrF]·BrF. It features molecular [(μ-F)(BrF)] anions of tetrahedron-like shape containing central μ-bridging F atoms coordinated by four BrF molecules. It is the most BrF-rich fluoridobromate anion by mass.

Direct Band Gap Semiconductors with Two- and Three-Dimensional Triel-Phosphide Frameworks (Triel=Al, Ga, In).

Recently, several ternary phosphidotrielates and -tetrelates have been investigated with respect to their very good ionic conductivity, while less focus was pointed towards their electronic structures. Here, we report on a novel series of compounds, in which several members possess direct band gaps. We investigated the known compounds LiAlP, LiGaP, LiInP, and NaInP and describe the synthesis and the crystal structure of novel NaInP.

Ba [BN ] H : A Disordered Anti-Skutterudite filled with Nitridoborate Anions.

Skutterudites are of high interest in current research due to their diversity of structures comprising empty, partially filled and filled variants, mostly based on metallic compounds. We herein present Ba [BN ] H , forming a non-metallic filled anti-skutterudite. It is accessed in a solid-state ampoule reaction from barium subnitride, boron nitride and barium hydride at 750 °C.

Evolutionary Algorithm-Based Crystal Structure Prediction of CuZnO Ternary Oxides.

Binary zinc(II) oxide (ZnO) and copper(II) oxide (CuO) are used in a number of applications, including optoelectronic and semiconductor applications. However, no crystal structures have been reported for ternary Cu-Zn-O oxides. In that context, we investigated the structural characteristics and thermodynamics of CuZnO ternary oxides to map their experimental feasibility.

Investigation on the predictive power of tolerance factor for A-site double perovskite oxides.

We have used a recently introduced new tolerance factor to create a stability map of all possible A-site double perovskite titanates AA'TiO and niobates AA'NbO. The predictive power of is relatively good based on comparisons with available experimental data for A-site double perovskites. We carried out quantum chemical calculations on two hypothetical double perovskite compositions CsScTiO and YRbTiO, where predicts high probability for their existence.

Discrete Mono-, Di-, and Trinuclear Anions [MoOF], [MoOF], [MoOF], [MoOF], [MoOF], and the Infinite Chain Anion [MoOF] Obtained from Reactions of MoOF: Synthesis and Analysis of the Structure-Chemical Relations of the Compounds.

The herein-reported oxyfluoridometallate salts were synthesized and structurally characterized during the studies of the Lewis acidity of OF ( = Mo, W) with various fluoride ion donors (RbF, CsF, TlF, AgF, SrF, BaF, PbF) in different solvents (aqHF 48%, aHF, BrF, ClF). Phase-pure MoOF was either synthesized by hydrolysis of MoF with SiO in anhydrous HF (aHF) or by reactions of BrF with MoO or MoO, respectively. The compound was characterized by infrared and Raman spectroscopy, solid-state quantum-chemical calculations, as well as powder and single-crystal X-ray diffraction.

(μ -F)(BrF ) ] - An Unprecedented Molecular Fluoridobromate(V) Anion in Cs[Br F.

The reaction of Cs[BrF ] with BrF gave the compound Cs[Br F ] with the unprecedented propeller-shaped, C -symmetric [(μ -F)(BrF ) ] anion. All other currently known fluoridobromates(V) contain only octahedral [BrF ] anions, which, unlike the related [IF ] anions, never exhibited stereochemical activity of the lone pair on the Br atoms. Despite the same coordination number of six for the Br atom in the [BrF ] and [(μ -F)(BrF ) ] anions, the longer μ -F-Br bonds provide additional space, allowing the lone pairs on the Br atoms to become stereochemically active.

Fast and Tunable Phosphorescence from Organic Ionic Crystals.

Crystalline diphosphonium iodides [MeR P-spacer-R Me]I with phenylene (1, 2), naphthalene (3, 4), biphenyl (5) and anthracene (6) as aromatic spacers, are photoemissive under ambient conditions. The emission colors (λ values from 550 to 880 nm) and intensities (Φ reaching 0.75) are defined by the composition and substitution geometry of the central conjugated chromophore motif, and the anion-π interactions.

Experimental and computational study of the role of defects and secondary phases on the thermoelectric properties of TiNiSn (0 ≤≤ 0.12) half Heusler compounds.

The half Heusler TiNiSn compound is a model system for understanding the relationship among structural, electronic, microstructural and thermoelectric properties. However, the role of defects that deviate from the ideal crystal structure is far from being fully described. In this work, TiNiSn alloys (= 0, 0.

Probing Charge-Transfer Processes in a Covalently Linked [Ge ]-Cluster Imine Dyad.

C donor dyads in which the carbon cage is covalently linked to an electron-donating unit have been discussed as one possibility for an electron-transfer system, and it has been shown that spherical [Ge ] cluster anions show a close relation to fullerenes with respect to their electronic structure. However, the optical properties of these clusters and of functionalized cluster derivatives are almost unknown. We now report on the synthesis of the intensely red [Ge ] cluster linked to an extended π-electron system.

Mechanical Properties of Polypropylene-Cellulose Biocomposites: Molecular Dynamics Simulations Combined with Constant Strain Method.

The use of biocomposites is increasing due to their recyclability, biodegradability, and decreased CO emission levels compared to pure polyolefin plastics. Furthermore, suitably engineered biocomposites can provide, for example, superior mechanical properties for various applications. However, the correlations between the atomic-level structure and mechanical properties of most biocomposites are not yet understood.

A Computational Study on Closed-Shell Molecular Hexafluorides MF (M=S, Se, Te, Po, Xe, Rn, Cr, Mo, W, U) - Molecular Structure, Anharmonic Frequency Calculations, and Prediction of the NdF Molecule.

Quantum chemical methods were used to study the molecular structure and anharmonic IR spectra of the experimentally known closed-shell molecular hexafluorides MF (M=S, Se, Te, Xe, Mo, W, U). First, the molecular structures and harmonic frequencies were investigated using Density Functional Theory (DFT) with all-electron basis sets and explicitly considering the influence of spin-orbit coupling. Second, anharmonic frequencies and IR intensities were calculated with the CCSD(T) coupled cluster method and compared, where available, with IR spectra recorded by us.

Hybrid Inorganic-Organic Complexes of Zn, Cd, and Pb with a Cationic Phenanthro-diimine Ligand.

The phosphonium-decorated phenanthro-imidazolyl pyridine ligand, Br, readily reacts with zinc(II) and cadmium(II) bromides to give inorganic-organic zero-dimensional compounds [ZnBr][ZnBr] () and [()CdBr][CdBr] (), respectively, upon crystallization. These salts are moderately fluorescent in the solid state under ambient conditions (λ = 458 nm, Φ = 0.11 for ; λ = 460 nm, Φ = 0.

Structural principles of cation ordering and octahedral tilting in A-site ordered double perovskites: ferroelectric CaMnTiO as a model system.

We have used quantum chemical methods to study the structural principles and energetics of A-site ordered AA'BO double perovskites. 33 combinations of A-site ordering and Glazer tilting have been systematically studied for the ferroelectric CaMnTiO model system. The used approach was able to predict the correct combination of A-site ordering and tilting of octahedra in comparison to the experimentally known CaMnTiO.

Thermodynamic Properties of Crystalline Cellulose Allomorphs Studied with Dispersion-Corrected Density Functional Methods.

The phonon properties and thermodynamics of four crystalline cellulose allomorphs, Iα, Iβ, II, and III1, have been investigated using dispersion-corrected density functional theory (DFT). In line with experimental findings, the free energy differences between the studied cellulose allomorphs are small, less than 1 kJ/mol per atom. The calculated specific heat at constant volume (Cv) has been compared with the available experimental data in the temperature range 10-300 K.

Molecular Dynamics Simulations on the Elastic Properties of Polypropylene Bionanocomposite Reinforced with Cellulose Nanofibrils.

Cellulose-reinforced polypropylene bionanocomposites can show improved elastic properties over their pure polypropylene counterparts. We have used equilibrium and non-equilibrium molecular dynamics (MD) simulations to study the elastic properties of polypropylene bionanocomposite systems composed of cellulose nanofibrils (CNF), polypropylene (PP) matrix, and maleic anhydride (MAH) coupling agent. The components of the bionanocomposite were parametrized for compatibility with the AMBER14SB force fields.

Bromine Pentafluoride BrF , the Formation of [BrF ] Salts, and the Stereochemical (In)activity of the Bromine Lone Pairs.

BrF can be prepared by treating BrF with fluorine under UV light in the region of 300 to 400 nm at room temperature. It was analyzed by UV-Vis, NMR, IR and Raman spectroscopy. Its crystal structure was redetermined by X-ray diffraction, and its space group was corrected to Pnma.