Synthesis and Characterization of [Fe3(As3)3(As4)]3−, a Binary Fe/As Zintl Cluster With an Fe3 Core

We report here the synthesis and structural characterization of the first binary iron arsenide cluster anion, [Fe₃(As₃)₃(As₄)]³⁻, present in both [K([2.2.2]crypt)]₃[Fe₃(As₃)₃(As₄)] ( 1 ) and [K(18-crown-6)]₃[Fe₃(As₃)₃(As₄)]⋅en ( 2 ). The cluster contains an Fe₃ triangle with three short Fe−Fe bond lengths (2.494(1) Å, 2.459(1) Å and 2.668(2) Å for 1 , 2.471(1) Å, 2.473(1) Å and 2.660(1) Å for 2 ), bridged by a 2-butene-like As₄ unit. An analysis of the electronic structure using DFT reveals a triplet ground state with direct Fe−Fe bonds stabilizing the Fe₃ core.     

Lattice distortions in layered type arsenides LnTAs2 (Ln=La-Nd, Sm, Gd, Tb; T=Ag, Au): Crystal structures, electronic and magnetic properties

The lanthanide coinage-metal diarsenides LnTAs₂ (Ln=La, Ce-Nd, Sm; T=Ag, Au) have been reinvestigated and their structures have been refined from single crystal X-ray data. Two different distortion variants of the HfCuSi₂ type are found: PrAgAs₂, NdAgAs₂, SmAgAs₂, GdAgAs₂, TbAgAs₂, NdAuAs₂ and SmAuAs₂ crystallize as twofold superstructures in space group Pmcn with the As atoms of their planar layers forming zigzag chains, whereas LaAgAs₂, CeAgAs₂ and PrAuAs₂ adopt a fourfold superstructure (space group Pmca) with cis-trans chains of As atoms. The respective atomic positions can be derived from the HfCuSi₂ type by group-subgroup relations. The compounds with zigzag chains of As atoms exhibit metallic behaviour while those with cis-trans chains are semiconducting as measured on powder pellets. The majority of the compounds including 4f elements show antiferromagnetic ordering at T_N<20 K.     

Structure determination of niobium palladium arsenide, Nb5Pd4As4, from a 5×5×5 μm crystal with synchrotron radiation

Niobium palladium arsenide, Nb₅Pd₄As₄, is the second phase found in the Nb-Pd-As system. It was synthesized by direct reaction of the elements and its crystal structure was determined from X-ray diffraction data obtained with synchrotron radiation on a 5×5×5 μm³ single crystal at 150 K. Nb₅Pd₄As₄ is isostructural to Nb₅Pd₄P₄ and adopts the Nb₅Cu₄Si₄-type structure (tetragonal, space group I4/m, Z=2, a=10.4457(17) Å, c=3.7868(6) Å). The structure can be described as being built up of As-centered trigonal prisms whose vertices are Nb and Pd atoms, or as chains of octahedral Nb₆ clusters embedded in As₈ cubes parallel to chains of edge-sharing tetrahedral Pd₄ clusters. Extended Hückel calculations show that metal-metal bonding constitutes the most important contribution to the stability of the structure, and that the Pd atoms are close to being zero-valent.     

77Se solid-state NMR investigations on As(x)Se(1-x) glasses using CPMG acquisition under MAS

⁷⁷Se (I=1/2) solid-state NMR is a very sensitive probe of the local structure of selenide glasses, which themselves are promising for optical applications. In this work, we show that although ⁷⁷Se has a low natural abundance (7.58%) and a wide spectral range, the sensitivity can be dramatically increased using Carr–Purcell–Meiboom–Gill (CPMG) trains of rotor-synchronized π pulses during the detection of ⁷⁷Se magnetization but may be affected by chemical shift anisotropy when the Magic Angle Spinning rate is not fast enough and by offset effects. The indirect dimension of the T₂^CPMG-resolved spectrum shows a strong influence of the J-couplings between naturally occurring ⁷⁷Se pairs. The resulting spectra show that the structural model known as “chains crossing model” is not entirely suitable to describe the glassy network of the Se-rich compositions.