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 Sc 5 P 12 N 23 O 3 and Ti 5 P 12 N 24 O 2 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. NH 4 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. Sc 5 P 12 N 23 O 3 and Ti 5 P 12 N 24 O 2 crystallize isotypically with Ti 5 B 12 O 26 , 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. Ti 5 P 12 N 24 O 2 is a mixedvalence compound and shows ordering of Ti 3 + and Ti 4 + ions.

The new semiconducting sodalite-type BaGe8As14 compound exhibits a narrow band gap, low resistivity and partially disordered atom positions as good prerequisites for a thermoelectric material.

The three‐dimensional SiP4 network in the known phosphidosilicate Ba2SiP4‐tI28 is analogous to β‐Cristobalite if oxygen is formally replaced by P–P dimers. Here we report a second polymorph Ba2SiP4‐oP56 [Pnma, a = 12.3710(4) Å, b = 14.6296(7) Å, c = 7.9783(3) Å; Z = 8] with chains of SiP4 tetrahedra connected by P–P bonds, reminiscent to the elusive fibrous SiO2. Ba2SiP4 is enantiotropic. The high temperature polymorph Ba2SiP4‐oP56 transforms to the low‐temperature phase Ba2SiP4‐tI28 at 650 °C and reconstructs to the high‐temperature modification at 1100 °C. DFT calculations predict an indirect optical bandgap of about 1.7 eV.

TiP4N8 was obtained from the binary nitrides TiN and P3N5 upon addition of NH4F 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 β‐TiP4N8, respectively. The structures of TiP4N8 exhibit body‐centered tetragonal (bct) framework topology. DFT calculations confirm the measured band gaps of α‐ and β‐TiP4N8 (1.6–1.8 eV) and predict the thermochemistry of the polymorphs in agreement with the experiments.

FeFe(Cl 2 -bdt)(CO) 6 ]( 1;C l 2 -bdt = 3,6-dichlorobenzene-1,2-dithiolate), inspired by the actives ite of FeFe-hydrogenase, shows ac hemically reversible 2e À reduction at À1.20 Vv ersus the ferrocene/ferrocenium couple. The rigid and aromatic bdt bridging ligand lowers the reductionp otential and stabilizes the reduced forms,c ompared with analogous complexes with aliphatic dithiolates;t husa llowing detailso ft he catalytic process to be characterized.Herein,t ime-resolved IR spectroscopy is used to provide kinetic and structurali nformation on key catalytic intermediates. This includes the doublyr educed, protonated complex 1H À ,w hich has not been previously identifiede xperimentally.I na ddition, the first direct spectroscopic observation of the turnoverp rocess for am olecular H 2 evolving catalysti s reported, allowing for straightforward determination of the turnover frequency.Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

The new lanthanum vanadium oxyselenides LaVSeO, LaVSeO, LaVSeO, LaVSeO, and LaVSeO were synthesized in eutectic NaI/KI fluxes, and their crystal structures were determined using single-crystal and powder X-ray diffraction experiments. LaVSeO and LaVSeO adopt known structure types, whereas LaVSeO, LaVSeO, and LaVSeO crystallize in hitherto unknown structure types. The main building blocks of these compounds are chains of edge-sharing VSe, VSeO, and/or VSeO octahedra, linked together by edge-sharing OLa and/or OLaV tetrahedra forming fluorite-like ribbons. LaVSeO, LaVSeO, and LaVSeO contain only V(iii) ions, whereby LaVSeO and LaVSeO 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 LaVSeO, metamagnetism for LaVSeO, ferromagnetism for LaVSeO and a complex magnetic structure for LaVSeO.

The three ligands, 1-cyclopropyl-5H-tetrazole (C3tz, 1), 1-cyclobutyl-5H-tetrazole (C4tz, 2), and 1-cyclopentyl-5H-tetrazole (C5tz, 3) were synthesized and used for the design of 19 new energetic coordination compounds (ECC) based on 3d...

The solid-state compounds M 15 Tr 22As32 and M 3Ga6As8 (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 (M 15 Tr 22As32) or T6 supertetrahedra (M 3Ga6As8), 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.