Effect of antifluorite layer on the magnetic order in Eu-based 1111 compounds, EuTAsF (T = Zn, Mn, and Fe).

The 1111 compounds with an alternating sequence of fluorite and antifluorite layers serve as structural hosts for the vast family of Fe-based superconductors. Here, we use neutron powder diffraction and density-functional-theory (DFT) band-structure calculations to study magnetic order of Eu2+ in the [EuF]+ fluorite layers depending on the nature of the [TAs]- antifluorite layer that can be non-magnetic semiconducting (T = Zn), magnetic semiconducting (T = Mn), or magnetic metallic (T = Fe). Antiferromagnetic transitions at TN ∼ 2.4-3 K due to an ordering of the Eu2+ magnetic moments were confirmed in all three EuTAsF compounds. Whereas in EuTAsF (T = Zn and Mn), the commensurate k1 = (½ ½ 0) stripe order pattern with magnetic moments within the a-b plane is observed, the order in EuFeAsF is incommensurate with k = (0 0.961(1) ½) and represents a cycloid of Eu2+ magnetic moments confined within the bc-plane. Additionally, the Mn2+ sublattice in EuMnAsF features a robust G-type antiferromagnetic order that persists at least up to room temperature, with magnetic moments along the c-direction. Although DFT calculations suggest stripe antiferromagnetic order in the Fe-sublattice of EuFeAsF as the ground state, neutron diffraction reveals no evidence of long-range magnetic order associated with Fe. We show that the frustrating interplane interaction J3 between the adjacent [EuF]+ layers is comparable with in-plane J1-J2 interactions already in the case of semiconducting fluorite layers [TAs]- (T = Zn and Mn) and becomes dominant in the case of the metallic [FeAs]- ones. The latter, along with a slight orthorhombic distortion, is proposed to be the origin of the incommensurate magnetic structure observed in EuFeAsF.

Synthesis, electronic structure and physical properties of two new layered compounds, EuFAgSe and EuFAg1-δTe, featuring the active redox pair Eu2+/Ag.

Systematic studies of the ZrCuSiAs (also LaOAgS or 1111) structure type resulted in the synthesis of two new fluoride chalcogenides, EuFAgSe and EuFAg1-δTe, whereas their sulfide analog, EuFAgS, could not be obtained. Both new compounds are tetragonal, P4/nmm, with cell parameters a = 4.1542(1) Å, c = 9.2182(1) Å for the selenide and a = 4.3255(1) Å, c = 9.5486(1) Å for the telluride. Rietveld refinement reveals a significant silver deficiency in the telluride (δ = 0.05), while the selenide is nearly stoichiometric. Both compounds are semiconductors as shown by diffuse reflectance spectroscopy and confirmed by density-functional calculations of the band structure. Magnetism of both compounds is predominantly driven by Eu2+, as indicated by magnetic susceptibility measurements and corroborated by 151Eu Mössbauer spectroscopy. EuFAg1-δTe and EuFAgSe are paramagnetic down to 1.8 K.

Pb6O5(NO3)2: A Nonlinear Optical Oxynitrate Structurally Based on Lead Oxide Framework.

A high second harmonic generation response is demonstrated by a Pb6O5(NO3)2 lead oxynitrate whose identity was verified upon reinvestigation of the PbO-Pb(NO3)2 system. Its crystal structure exhibits a unique cationic [Pb6O5]2+ framework hosting orientationally ordered NO3- triangles in the channels. Easy preparation and high thermal stability (until ∼500 °C in air) suggest it to be a new promising NLO material.

Synthesis, crystal and electronic structures of Pt-rich phosphides EuPt3P and EuPt6P2.

Two new ternary Pt-rich phosphides, EuPt6P2 and EuPt3P, have been prepared via a two-step solid state reaction. Their crystal structures have been determined from powder XRD data. EuPt6P2 is isostructural to SrPt6P2 (cubic, Pa3[combining macron], a = 8.4603(1) Å); its crystal structure comprises corner-sharing Pt6P trigonal prisms hosting Eu2+ cations in the cuboctahedral voids of the framework. EuPt3P is isostructural to the SrPt3P anti-perovskite (P4/nmm, a = 5.7452(1) Å and c = 5.4212(1) Å). Magnetization measurements reveal the magnetic response caused by the Eu2+(4f7) cations. EuPt6P2 is paramagnetic exhibiting no phase transitions down to 1.8 K, whereas EuPt3P orders ferromagnetically below 19 K. Similar to SrPt6P2 and SrPt3P, the new compounds are metallic with states near the Fermi level predominantly formed by the 5d orbitals of Pt.

Layered Compounds BaFMgPn (Pn = P, As, Sb, and Bi), Transition-Metal-Free Representatives of the 1111 Structure Type.

Four new transition metal-free pnictide representatives of the LaOAgS structure type were predicted by DFT calculations and found in the BaFMgPn (Pn = P, As, Sb and Bi) family. The compounds adopt the tetragonal space group P4 /nmm with the unit cell parameters a/ c 4.3097(1) Å/9.5032(1) Å, 4.3855(1) Å/9.5918(1) Å, 4.5733(1) Å/9.8184(1) Å, and 4.6359(1) Å/9.8599(1) Å, respectively. According to the DFT calculations, these new compounds are semiconductors with band gaps steadily decreasing from Pn = P ( ca. 2 eV) to Pn = Bi ( ca. 1 eV). The corresponding strontium fluoride and rare-earth oxide analogs are unlikely to exist and have not been observed yet. The trends of the stability within 1111 and structurally and/or chemically related compounds based on a combined consideration of geometry and DFT calculations are discussed.

Structural and Thermodynamic Stability of the "1111" Structure Type: A Case Study of the EuFZnPn Series.

Two new compounds with the LaOAgS structure, EuFZnAs (1) and EuFZnSb (2), were obtained via solid state reaction. Both compounds are tetragonal (P4/nmm) with the cell parameters a = 4.1000(1) Šand c = 9.0811(1) Šfor 1 and a = 4.2852(1)Šand c = 9.4238(1)Šfor 2. The absence of their phosphide analog can be explained based on crystal chemical considerations as well as on quantum-chemical estimates of their thermodynamic stability with respect to EuF2 and EuZn2Pn2. The magnetic response of 1 and 2 is ascribed to the presence of Eu2+ ions. Both compounds are paramagnetic down to low temperatures, where they order antiferromagnetically at ∼5 K and ∼3 K, respectively. They are narrow-gap semiconductors, and EuFZnSb demonstrates a relatively high value of the Seebeck coefficient.

Effect of Transition Metal Substitution on the Structure and Properties of a Clathrate-Like Compound Eu7Cu44As23.

A series of substitutional solid solutions-Eu7Cu44-xTxAs23 (T = Fe, Co, Ni)-based on a recently discovered clathrate-like compound (Eu7Cu44As23) were synthesized from the elements at 800 °C. Almost up to 50% of Cu can be substituted by Ni, resulting in a linear decrease of the cubic unit cell parameter from a = 16.6707(1) Å for the ternary compound to a = 16.3719(1) Å for the sample with the nominal composition Eu7Cu24Ni20As23. In contrast, Co and Fe can only substitute less than 20% of Cu. Crystal structures of six samples of different composition were refined from powder diffraction data. Despite very small differences in scattering powers of Cu, Ni, Co, and Fe, we were able to propose a reasonable model of dopant distribution over copper sites based on the trends in interatomic distances as well as on Mössbauer spectra for the iron-substituted compound Eu7Cu36Fe8As23. Ni doping increases the Curie temperature to 25 K with respect to the parent compound, which is ferromagnetically ordered below 17.5 K, whereas Fe doping suppresses the ferromagnetic ordering in the Eu sublattice.

Two new arsenides, Eu7Cu44As23 and Sr7Cu44As23, with a new filled variety of the BaHg11 structure.

Two new ternary arsenides, namely, Eu7Cu44As23 and Sr7Cu44As23, were synthesized from elements at 800 °C. Their crystal structure represents a new filled version of the BaHg11 motif with cubic voids alternately occupied by Eu(Sr) and As atoms, resulting in a 2 × 2 × 2 superstructure of the aristotype: space group Fm3̅m, a = 16.6707(2) Å and 16.7467(2) Å, respectively. The Eu derivative exhibits ferromagnetic ordering below 17.5 K. In agreement with band structure calculations both compounds are metals, exhibiting relatively low thermopower, but high electrical and low thermal conductivity.