Discovery of Two Polymorphs of TiP4 N8 Synthesized from Binary Nitrides.

TiP4 N8 was obtained from the binary nitrides TiN and P3 N5 upon addition of NH4 F as a mineralizer at 8 GPa and 1400 °C. An intricate interplay of disorder and polymorphism was elucidated by in situ temperature-dependent single-crystal X-ray diffraction, STEM-HAADF, and the investigation of annealed samples. This revealed two polymorphs, which consist of dense networks of PN4 tetrahedra (degree of condensation κ=0.5) and either augmented triangular TiN7 prisms or triangular TiN6 prisms for α- and ß-TiP4 N8 , respectively. The structures of TiP4 N8 exhibit body-centered tetragonal (bct) framework topology. DFT calculations confirm the measured band gaps of α- and ß-TiP4 N8 (1.6-1.8 eV) and predict the thermochemistry of the polymorphs in agreement with the experiments.

High-Pressure Synthesis of Sc5 P12 N23 O3 and Ti5 P12 N24 O2 by Activation of the Binary Nitrides ScN and TiN with NH4 F.

Multinary transition metal nitrides and oxonitrides are a versatile and intriguing class of compounds. However, they have been investigated far less than pure oxides. The compounds Sc5 P12 N23 O3 and Ti5 P12 N24 O2 have now been synthesized from the binary nitrides ScN and TiN, respectively, by following a high-pressure high-temperature approach at 8 GPa and 1400 °C. NH4 F acts as a mineralizing agent that supports product formation and crystallization. The starting materials ScN and TiN are seemingly an uncommon choice because of their chemical inertness but, nevertheless, react under these conditions. Sc5 P12 N23 O3 and Ti5 P12 N24 O2 crystallize isotypically with Ti5 B12 O26 , consisting of solely vertex-sharing P(O/N)4 tetrahedra forming two independent interpenetrating diamond-like nets that host TM(O/N)6 (TM=Sc, Ti) octahedra. Ti5 P12 N24 O2 is a mixed-valence compound and shows ordering of Ti3+ and Ti4+ ions.

BaGe8As14: a semiconducting sodalite-type compound.

A new sodalite-type compound, namely BaGe8As14 was synthesized via solid-state reactions and structurally characterized with single crystal X-ray diffraction (space group I4[combining macron]3m). Vertex-sharing GeAs4-tetrahedra form ß-cages with additional Ge/As-mixed sites located slightly above or below the six-membered rings. The structure is similar to the borate mineral rhodizite. Barium atoms are disordered due to a slight shift off the centers of large ß-cages. This partially disordered structure together with a narrow bandgap of 0.43 eV in line with low resistivity (2 × 10-2Ω cm), and a high carrier concentration (1.6 × 1020 cm-3) at 300 K qualifies BaGe8As14 as a potential thermoelectric material.

Mixed Valence and Unusual Germanium Coordination in SrGe8As10, BaGe8As10, and BaGe7P12.

The new Zintl-compounds AEGe8As10 (AE = Sr, Ba) and BaGe7P12 were synthesized via solid-state reactions, and their structures were determined by single crystal and powder X-ray diffraction. SrGe8As10 and BaGe8As10 crystallize in the space group Cmce and show complex 3D networks composed of three different Ge-As motifs and As-As bonds with mixed valence of germanium in the oxidation states +2, + 3, and +4. Mixed valences of germanium +3 and +4 occur in BaGe7P12, which crystallizes in the space group R3̅ with a 3D network built up of Ge2P6 dumbbells and P-P bonds. An exceptional 6-fold coordinated germanium resides in the center of a GeP6 trigonal antiprism. High temperature X-ray diffraction shows thermal stabilities up to 923-953 K. UV-Vis and resistivity measurements reveal a semiconducting nature with small indirect band gaps between 0.02 and 1.6 eV. Electronic band structure calculations confirm the semiconducting state and indicate covalent bonds within the Ge-Pn polyanions.

High-pressure synthesis and crystal structure of SrGa4As4.

Strontium tetra-gallate(II,III) tetra-arsenide, SrGa4As4, was synthesized in a Walker-type multianvil apparatus under high-pressure/high-temperature conditions of 8 GPa and 1573 K. The com-pound crystallizes in a new structure type (P3221, Z = 3) as a three-dimensional (3D) framework of corner-sharing SrAs8 quadratic anti-prisms with strontium situated on a twofold rotation axis (Wyckoff position 3b). This arrangement is surrounded by a 3D framework which can be described as alternately stacked layers of either condensed GaIIIAs4 tetra-hedra or honeycomb-like layers built up from distorted ethane-like GaII 2As6 units com-prising Ga-Ga bonds.

Supertetrahedral Layers Based on GaAs or InAs.

The solid-state compounds M15Tr22As32 and M3Ga6As8 (M = Sr, Eu; Tr = Ga, In) were synthesized by heating the elements, and their crystal structures were determined by single-crystal and powder X-ray diffraction (space group C2/c). The structures are hierarchical variants of the HgI2 type and consist of layers of polymeric T5 (M15Tr22As32) or T6 supertetrahedra (M3Ga6As8), separated by strontium or europium cations. These compounds constitute hitherto unknown GaAs- or InAs-based supertetrahedral structures and represent the first binary vacancy-free T5 and T6 supertetrahedra. Vacancies or mixed-metal strategies for charge compensation, as known from related chalcogenides, are not required for supertetrahedra based on charge-neutral GaAs or InAs. Optical band gap, resistivity, and Hall-effect measurements together with DFT calculations reveal that the supertetrahedral compounds are direct band gap semiconductors similar to binary GaAs or InAs. Magnetic susceptibility measurements confirm Eu2+ in Eu15Ga22As32, Eu15In22As32, and Eu3Ga6As8 and indicate antiferromagnetic ordering below 10 K.

Direct Spectroscopic Detection of Key Intermediates and the Turnover Process in Catalytic H2 Formation by a Biomimetic Diiron Catalyst.

[FeFe(Cl2 -bdt)(CO)6 ] (1; Cl2 -bdt=3,6-dichlorobenzene-1,2-dithiolate), inspired by the active site of FeFe-hydrogenase, shows a chemically reversible 2 e- reduction at -1.20 V versus the ferrocene/ferrocenium couple. The rigid and aromatic bdt bridging ligand lowers the reduction potential and stabilizes the reduced forms, compared with analogous complexes with aliphatic dithiolates; thus allowing details of the catalytic process to be characterized. Herein, time-resolved IR spectroscopy is used to provide kinetic and structural information on key catalytic intermediates. This includes the doubly reduced, protonated complex 1H- , which has not been previously identified experimentally. In addition, the first direct spectroscopic observation of the turnover process for a molecular H2 evolving catalyst is reported, allowing for straightforward determination of the turnover frequency.

Flux synthesis, crystal structures, and physical properties of new lanthanum vanadium oxyselenides.

The new lanthanum vanadium oxyselenides LaVSe2O, La5V3Se6O7, La5V3Se7O5, La7VSe5O7, and La13V7Se16O15 were synthesized in eutectic NaI/KI fluxes, and their crystal structures were determined using single-crystal and powder X-ray diffraction experiments. LaVSe2O and La5V3Se6O7 adopt known structure types, whereas La5V3Se7O5, La7VSe5O7, and La13V7Se16O15 crystallize in hitherto unknown structure types. The main building blocks of these compounds are chains of edge-sharing VSe6, VSe5O, and/or VSe4O2 octahedra, linked together by edge-sharing OLa4 and/or OLa3V tetrahedra forming fluorite-like ribbons. LaVSe2O, La5V3Se7O5, and La7VSe5O7 contain only V(iii) ions, whereby La5V3Se6O7 and La13V7Se16O15 contain mixtures of either V(iii)/V(iv) or V(iii)/V(v) cations. Magnetic measurements indicate Curie-Weiss paramagnetism and magnetic ordering of the vanadium moments at low temperatures. More precisely, we observe antiferromagnetism for La5V3Se6O7, metamagnetism for La5V3Se7O5, ferromagnetism for La7VSe5O7 and a complex magnetic structure for La13V7Se16O15.

Flux Synthesis, Crystal Structures, and Magnetic Ordering of the Rare-Earth Chromium(II) Oxyselenides RE2CrSe2O2 (RE = La-Nd).

The rare-earth chromium(II) oxyselenides RE2CrSe2O2 (RE = La-Nd) were synthesized in eutectic NaI/KI fluxes, and their crystal structures were determined by single-crystal and powder X-ray diffraction (Pb2HgCl2O2-type, C2/m, Z = 2). The magnetic structure of La2CrSe2O2 was solved and refined from neutron powder diffraction data. Main building blocks are chains of edge-sharing CrSe4O2 octahedra linked together by two edge-sharing ORE3Cr tetrahedra forming infinite ribbons. The Jahn-Teller instability of divalent Cr2+ (d4) leads to structural phase transitions at 200 and 130 K in La2CrSe2O2 and Ce2CrSe2O2, respectively. RE2CrSe2O2 are Curie-Weiss paramagnetic above TN ≈ 14-17 K. Neutron powder diffraction reveals anti-ferromagnetic ordering of the Cr2+ moments in La2CrSe2O2 below TN = 12.7(3) K with an average ordered moment of 3.40(4) µB/Cr2+ at 4 K, which was confirmed by muon spin rotation experiments.