REAuAl4Ge2 and REAuAl4(AuxGe1−x)2 (RE=rare earth element): Quaternary intermetallics grown in liquid aluminum

The two families of intermetallic phases REAuAl₄Ge₂ (1) (RE=Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm and Yb) and REAuAl₄(Au_xGe_1−x)₂ (2) (x=0.4) (RE=Ce and Eu) were obtained by the reactive combination of RE, Au and Ge in liquid aluminum. The structure of (1) adopts the space group R-3m (CeAuAl₄Ge₂, , ; NdAuAl₄Ge₂, , ; GdAuAl₄Ge₂, , ; ErAuAl₄Ge₂, , ). The structure of (2) adopts the tetragonal space group P4/mmm with lattice parameters: , for EuAuAl₄(Au_xGe_1−x)₂ (x=0.4). Both structure types present slabs of “AuAl₄Ge₂” or “AuAl₄(Au_xGe_1−x)₂” stacking along the c-axis with layers of RE atoms in between. Magnetic susceptibility measurements indicate that the RE atoms (except for Ce and Eu) possess magnetic moments consistent with +3 species. The Ce atoms in CeAuAl₄Ge₂ and CeAuAl₄(Au_xGe_1−x)₂ (x=0.4) appear to be in a mixed +3/+4 valence state; DyAuAl₄Ge₂ undergoes an antiferromagnetic transition at 11 K and below this temperature exhibits metamagnetic behavior. The Eu atoms in EuAuAl₄(Au_xGe_1−x)₂ (x=0.4) appear to be in a 2+ oxidation state.     

Synthesis and NMR spectroscopic investigation of salts containing the novel [Au(CF3)nX4−n] (n=4-1, X=F, CN, Cl) anions

First examples for the syntheses of trifluoromethyl transition metal complexes by conversion of a cyano into a trifluoromethyl ligand are described. The fluorination of [][Au(CN)₄] with ClF in CH₂Cl₂ leads to the formation of a mixture of gold complexes of the type [AuF_xCl_y(CF₃)_4−x−y]⁻ (x=0-4, y=0-2). Ligand exchange reactions of [AuF_xCl_y(CF₃)_4−x−y]⁻ (x=0-4, y=0-2) with (CH₃)₃SiY (Y=Cl, CN) are performed resulting in anions of the type [AuY_x(CF₃)_4−x]⁻ (x=0-4). All products are characterised by - and NMR spectroscopy.     

Structure and magnetic properties of sulfides of the type CdRE2S4 and Mg(GdxYb1−x)2S4

CdRE₂S₄ (RE = Gd, Tb, Dy, Ho, Er, Tm, and Yb) and Mg(Gd_xYb_1?x)₂S₄ were prepared by solid-state reactions. All the cadmium-containing compounds are cubic, i.e., the Th₃P₄ structure for Gd, Tb, and Dy and the spinel type for all the others. The first three compounds were deficient in CdS. In the case of the Mg system, for x = 1 the system is cubic Th₃P₄, for x = 0 cubic spinel, and for 0 < x < 1 orthorhombic MnY₂S₄ (Cmc2₁). All the materials studied are paramagnetic above 77 K. Below 77 K in the magnesium family both cubic materials are paramagnetic down to 4.2 K and the orthorhombic materials show magnetic ordering. In the cadmium family all but CdTm₂S₄ show exchange coupling.     

O MAS NMR study of the oxygen local environments in the anionic conductors Y2(B1−xB′x)2O7(B, B′=Sn, Ti, Zr)

The local environments for oxygen in yttrium-containing pyrochlores and fluorites, Y₂(B_1−xB′_x)₂O₇ (B=Ti, B′=Sn, Zr) are investigated by using solid state ¹⁷O MAS NMR spectroscopy. The quadrupolar coupling constants of the nucleus, ¹⁷O are sufficiently small for these ionic oxides, that high-resolution spectra are obtained from the MAS spectra. Different oxygen NMR resonances are observed due to local environments with differing numbers of metal cations (Y³⁺, Sn⁴⁺, Ti⁴⁺ and Zr⁴⁺), allowing the numbers of different local environments to be quantified and cation mixing to be investigated. Evidence for pyrochlore-like local ordering is detected for Y₂Zr₂O₇, which nominally adopts the fluorite structure.     

Interactions of Ba2YCu3O6+y with the Gd3NbO7 buffer layer in coated conductors

A systematic study of the chemical interaction of Ba₂YCu₃O_6+y and Gd₃NbO₇ was conducted under two processing conditions: purified air (21% p_o2), and 100 Pa p_o2 (0.1% p_o2). Phases present along the pseudo-binary join Ba₂YCu₃O_6z and Gd₃NbO₇ were found to be in two five-phase volumes within the system. Three common phases that are present in all samples are (Y,Gd)₂Cu₂O₅, Ba(Y,Gd)₂CuO₅ and Cu₂O or CuO (depending on the processing conditions). The assemblies of phases can be categorized in three regions, with Ba₂YCu₃O_6+y: Gd₃NbO₇ ratios of (I)<5.5:4.5; (II)=5.5:4.5; and (III)>5.5:4.5. The lowest melting temperature of the system was determined to be ≈938 °C in air, and 850 °C at 100 Pa p_o2. Structure determinations of two selected phases, Ba₂(Gd_xY_1−x)NbO₆ (Fm3¯m, No. 225), and (Gd_xY_3−x)NbO₇ (C222₁, No. 20 and Ccmm, No. 63), were completed using the X-ray Rietveld refinement technique. Reference X-ray powder diffraction patterns for selected phases of Ba₂(Gd_xY_1−x)NbO₆ (x=0.2, 0.4, 0.6, and 0.8) and (Gd_xY_3−x)NbO₇ (x=0.6, 1.2, 1.8, 2.4 and 3) have been prepared for inclusion in the Powder Diffraction File (PDF).     

Synthesis and magnetic properties of the quasi-one-dimensional compound Ca0.83(Cu1−xCox)O2

A new solid solution of the quasi-one-dimensional composite crystal, , has been synthesized under of O₂ at 830°C. The non-doped compound Ca_0.83CuO₂ consists of two interpenetrating monoclinic subsystems of the [Ca] atoms and the edge-shared square planar [CuO₂] chains. Upon increasing x, both the subsystems undergo a phase change from monoclinic to orthorhombic (M-O). The M-O change occurs at x∼0.04 for the [(Cu,Co)O₂] subsystem, while such a change occurs at x∼0.17 for the [Ca] subsystem. Magnetic susceptibility measurements show an evolution from a short-range ordered state near x=0 to a long-range antiferromagnetic state for the samples with x?0.15. The effective magnetic moment μ_eff is found to increase with increasing x from for x=0.10 to for x=0.30, suggesting that the solid solution can be regarded as Ca_0.83[Cu_0.66²⁺Cu_0.34−x³⁺Co_x³⁺]O₂, in which a mixed state of Cu²⁺(S=1/2), Cu³⁺(S=0) and high-spin Co³⁺(S=2) ions is realized.     

[Bi6O4.5(OH)3.5]2(NO3)11: a new anhydrous bismuth basic nitrate. Synthesis and structure determination from twinned crystals

The bismuth basic nitrate [Bi₆O_4.5(OH)_3.5]₂(NO₃)₁₁ crystallizes in the monoclinic space group P2₁ with , , , β=107.329(17)° and . Its structure has been determined from , twinned crystal X-ray data (16 781 reflections, 683 parameters, R=0.0703). It is built upon [Bi₆O_x(OH)_8−x]^(10−x)+, x=4 and x=5 hexanuclear complexes and nitrate groups. The polycationic entities are linked to the nitrate anions either by hydrogen bonds or through bismuth-oxygen coordination. Even at , the [Bi₆O₄(OH)₄]⁶⁺ and [Bi₆O₅(OH)₃]⁵⁺ polycations could not be observed as such, the crystal structure refinement only detecting an average [Bi₆O_4.5(OH)_3.5]^5.5+ polycation. To prove the presence of both hexanuclear complexes in the structure, we report the existence of a correlation between the bismuth-linked oxygen bond-valence parameters and the presence, or not, of hydroxyl groups. Moreover, the Raman spectrum of the new anhydrous bismuth basic nitrate is compared to those of [Bi₆O₅(OH)₃](NO₃)₅·3H₂O, [Bi₆O₄(OH)₄](NO₃)₆·4H₂O, and two yet uncharacterized bismuth nitrates.     

Non-stoichiometric 1:2 ordered perovskites in the Ba(Li1/4Nb3/4)O3-Ba(Li2/5W3/5)O3 system

Although both end members in the (1−x)Ba(Li_1/4Nb_3/4)O₃-xBa(Li_2/5W_3/5)O₃ (BLNW) system adopt a hexagonal perovskite structure, B-site ordered cubic perovskites are formed for the majority of their solid solutions (0.238?x?0.833). Within this range, single-phase 1:2 order (, , ) is stabilized for 0.238?x?0.385. In contrast to all known A(B_1/3^IB_2/3^II)O₃ perovskites, the 1:2 ordered BLNW solid solutions do not include any composition with a 1:2 cation distribution and the structure exhibits extensive non-stoichiometry. Structure refinements support a model where Li and W occupy different positions and Nb is distributed on both sites, i.e. Ba[(Li_3/4+y/2Nb_1/4−y/2)_1/3(Nb_1−yW_y)_2/3]O₃ (y=0.21-0.35, where y=0.9x). The stabilization of the non-stoichiometric order arises from the large charge/size site differences; the loss of 1:2 order for W-rich compositions is related to local charge imbalances on the A-site sub-lattice. The range of single-phase 1:1 order is confined to x=0.833, (Ba(Li_3/4Nb_1/4)_1/2(W)_1/2)O₃), where the site charge/size difference is maximized and the on-site mismatches are minimized. The microwave dielectric loss properties of the ordered BLNW solid solutions are significantly inferior as compared to their stoichiometric counterparts.     

Crystal structures, physical properties and NMR experiments on the ternary rare-earth metal silicide boride compounds RE5Si2B8 (RE=Y, Sm, Gd, Tb, Dy, Ho)

The ternary rare-earth metal silicide borides RE₅Si₂B₈ (RE=Y, Sm, Gd, Tb, Dy Ho) were prepared by arc melting the elemental components and subsequent annealing up to . The crystal structure was determined for each term of the series from single-crystal X-ray data: tetragonal symmetry, space group P4/mbm, Z=2; unit cell parameters a=7.2616(3), and a=7.1830(2), for Sm₅Si₂B₈ and Ho₅Si₂B₈, respectively. The structure is a new type and can be structurally described as an intergrowth of ThB₄-like and U₃Si₂-like slabs of composition REB₄ and RE₃Si₂, respectively, alternating along the c direction. The boron and silicon substructures are wholly independent and well ordered. The magnetic properties are as follows: Y₅Si₂B₈ is a Pauli-type paramagnet above 1.8 K, Gd₅Si₂B₈ undergoes a weak (canted) ferromagnetic-like order at 70 K followed by a colinear antiferromagnetic spin alignment at 44 K. Tb₅Si₂B₈ and Dy₅Si₂B₈ order antiferromagnetically at a Néel temperature of T_N=45 and 28 K, respectively. In the paramagnetic regime, the effective moments are in good accord with the theoretical RE³⁺ free ion moments. The temperature dependence of the electrical resistivities for the Y, Gd, Tb, and Dy containing samples corroborates with the metallic state of the nonmagnetic (Y) and the magnetically ordered compounds. ¹¹B, ²⁹Si and ⁸⁹Y nuclear magnetic resonance (NMR) spectroscopy on nonmagnetic Y₅Si₂B₈ shows different signals, which correspond to the expected number of distinct crystallographic sites in the structure. ¹¹B NMR on Y₅Si₂B₈ indicates that the local magnetic susceptibilities are substantially different from the ones observed in the related compound YB₄.     

Ordered perovskites in the A(Li1/4Nb3/4)O3-A(Li2/5W3/5)O3 (A=Sr, Ca) systems

Single-phase 1:2 B-site ordered perovskites are formed in the (1−x)A²⁺(Li_1/4Nb_3/4)O₃-(x)A²⁺(Li_2/5W_3/5)O₃ systems, A²⁺=Sr and Ca, within the range 0.238?x?0.333. The X-ray and electron diffraction patterns are consistent with a P2₁/c monoclinic supercell, , , , β≈125°, where the 1:2 order is combined with b⁻b⁻c⁺ octahedral tilting. Rietveld refinements of the ordered A(B^I_1/3B^II_2/3)O₃ structures give a good fit to a model with B^I occupied by Li and Nb, B^II by W and Nb, and a general stoichiometry (Sr,Ca)(Li_3/4+y/2Nb_1/4−y/2)_1/3(Nb_1−yW_y)_2/3O₃, y=0.9x=0.21-0.30. The Sr system also includes regions of stability of a 1:3 ordered phase for 0.0?x?0.111, and a 1:1 ordered double perovskite for 0.833?x?1.0. The formation of the non-stoichiometric 1:2 ordered phases is associated with the large site charge/size differences that can be accessed in these systems, and restricted by local charge imbalances at the A-sites for W-rich compositions. These concepts are used to generate stability maps to rationalize the formation of the known 1:2 ordered oxide perovskites.     

Three-dimensional framework of uranium-centered polyhedra with non-intersecting channels in the uranyl oxy-vanadates A2(UO2)3(VO4)2O (A=Li, Na)

The uranyl vanadates A₂(UO₂)₃(VO₄)₂O (A=Li, Na) have been synthesized by solid-state reaction and the structure of the Li compound was solved from single-crystal X-ray diffraction. The crystal structure is built from chains of edge-shared U(2)O₇ pentagonal bipyramids alternatively parallel to - and -axis and further connected together to form a three-dimensional (3-D) arrangement. The perpendicular chains are hung on both sides of a sheet parallel to (001), formed by U(1)O₆ square bipyramids connected by VO₄ tetrahedra, and derived from the autunite-type sheet. The resulting 3-D framework creates non-intersecting channels running down the - and -axis formed by empty face-shared oxygen octahedra, the Li⁺ ions are displaced from the center of the channels and occupy the middle of one edge of the common face. The peculiar position of the Li⁺ ion together with the full occupancy explain the low conductivity of Li₂(UO₂)₃(VO₄)₂O compared with that of Na(UO₂)₄(VO₄)₃ containing the same type of channels half occupied by Na⁺ ions in the octahedral sites.Crystallographic data for Li₂(UO₂)₃(VO₄)₂O: tetragonal, space group I41/amd, , , , Z=4, ρ_mes=5.32(2) g/cm³, ρ_cal=5.36(3) g/cm³, full-matrix least-squares refinement basis on F² yielded, R₁=0.032, wR₂=0.085 for 37 refined parameters with 364 independent reflections with I?2σ(I).     

Hydrothermal synthesis and characterization of a new 3D vanadium(III) phosphite (C4H8N2H4)0.5(C4H8N2H3)[V4(HPO3)7(H2O)3]1.5H2O

A new vanadium(III) phosphite, (C₄H₈N₂H₄)_0.5(C₄H₈N₂H₃)[V₄(HPO₃)₇(H₂O)₃]1.5H₂O, has been synthesized hydrothermally by using V₂O₅, H₃PO₃ as reactants, piperazine as the structure-directing agent. The as-synthesized product was characterized by powder X-ray diffraction, IR spectroscopy, inductively coupled plasma analysis, thermogravimetric analysis, and SQUID magnetometer. Single-crystal X-ray diffraction analysis shows that the title compound crystallized in the trigonal space group (No. 165) with the parameters: , , and Z=4. Its structure is built up by alternation of octahedral VO₆ or VO₅(H₂O) and pseudo-pyramidal HPO₃ units to form infinite 2D layers, and these layers are interconnected by sharing vertex-oxygen with octahedral VO₆ units to generate a 3D open-framework structure with 12-membered ring channels in a and b directions, respectively, where there exist entrapped diprotonated and mono-protonated piperazine cations, and water molecules. Magnetic measurement indicates that paramagnetic behavior is observed down to 4 K.     

Multianvil high-pressure/high-temperature preparation, crystal structure, and properties of the new oxoborates Dy4B6O14(OH)2 and Ho4B6O14(OH)2

This paper reports about two new hydrogen-containing rare-earth oxoborates RE₄B₆O₁₄(OH)₂ (RE=Dy, Ho) synthesized under high-pressure/high-temperature conditions from the corresponding rare-earth oxides, boron oxide, and water using a Walker-type multianvil equipment at 8 GPa and 880 °C. The single crystal structure determination of Dy₄B₆O₁₄(OH)₂ showed: Pbcn, a=1292.7(2), b=437.1(2), , Z=2, R1=0.0190, and wR2=0.0349 (all data). The isotypic holmium species revealed: Pbcn, a=1292.8(2), b=436.2(2), , Z=2, R1=0.0206, and wR2=0.0406 (all data). The compounds exhibit a new type of structure, which is built up from layers of condensed BO₄-tetrahedra. Between the layers, the rare-earth cations are coordinated by 7+2 oxygen atoms. Furthermore, we report about temperature-resolved in situ powder diffraction measurements, DTA/TG, and IR-spectroscopic investigations into RE₄B₆O₁₄(OH)₂ (RE=Dy, Ho).     

Correlation between structure and magnetic properties of Cd-substituted La0.7(Ca0.3−xCdx)MnO3 CMR manganites

Structural, electrical and magnetic properties of Cd-doped La_0.7(Ca_0.3−xCd_x)MnO₃ (0?x?0.3) manganites are presented. All compositions were indexed in the orthorhombic (Pnma) space group, except the Cd_0.3 sample, indexed as a combination of trigonal and orthorhombic (Pnma) space groups. Substitution of Ca by Cd has a strong influence on the magnetic and magnetoresistive properties of these compounds, continuously decreasing both the magnetic moment and the Curie temperature (from 3.5 μ_B and 270 K for the x=0 composition to 1.59 μ_B and 90 K for the fully doped x=0.3 one). Samples corresponding to x=0 and 0.1 show a semiconductor-metal transition at temperatures close to the Curie ones. The measured magnetoresistance change is about 49% at 270 K and 95% at 165 K for those samples, respectively. However, the x=0.2 and 0.3 compositions show insulating behaviour in the whole temperature range studied, with values of the magnetoresistance about 85% at 105 K and 74% at 90 K, respectively. The observed weakening of the double-exchange mechanism as the Cd doping level in these samples increases is discussed in terms of structural properties, cationic disorder and Mn³⁺/Mn⁴⁺content ratio.     

Hydrothermal synthesis and characterization of (enH2)3.5[As8V14O42(PO4)]·2H2O

The compound (enH₂)_3.5[As₈V₁₄O₄₂(PO₄)]·2H₂O 1 (en=ethylenediamine) has been synthesized and characterized by means of elemental analysis, IR spectrum, ESR spectrum, XPS spectrum, TG analysis and single crystal X-ray diffraction analysis. The compound 1 crystallizes in monoclinic system, space group C2/c, β=105.59(3), Z=8 and R₁(wR₂)=0.0398(0.0885). The compound 1 is constructed from [As₈V₁₄O₄₂(PO₄)]⁷⁻ anions and H₂en cations linked through hydrogen bonds into a network. The [As₈V₁₄O₄₂(PO₄)]⁷⁻ cluster consists of 14 VO₅ square pyramids linked by 4 As₂O₅ handle-like units, and includes at its center an ordered PO₄³⁻ anion.     

Epitaxial stabilization of (110)-layered perovskites of the RE2Ti2O7 (RE=La, Nd, Sm, Gd) family

Thin films of RE₂Ti₂O₇ (RE=La, Nd, Sm, Gd) were deposited on single crystal SrTiO₃ (110) substrates at 900 °C using pulsed laser deposition. X-ray diffraction (XRD) results showed sharp (00k) peaks (in θ-2θ scans) with narrow rocking curves (ω-scan peak widths of 0.4-0.9°), indicating that all compositions adopted the (110)-layered perovskite structure. While this is the stable structure for RE=La and Nd, it is metastable for RE=Sm and Gd. The metastable compounds are formed directly through epitaxial stabilization at these high temperatures and are shown to be isostructural to monoclinic La₂Ti₂O₇. The a, b, and c lattice parameters decreased monotonically with decreasing size of the RE cation, while the monoclinic angle remained fairly constant. The epitaxial relationship between the (110)-layered RE₂Ti₂O₇ films and the SrTiO₃(110) substrate was found by XRD and transmission electron microscopy to be . The single-phase, metastable, epitaxial, 100 nm thick films maintained the layered perovskite structure even after annealing at 900 °C for two hours in 200 Torr of oxygen.     

Structural aspects of Pr1−xSrxFeO3−w

Structural aspects of the distorted perovskite ABO₃ phase Pr_1−xSr_xFeO_3−w,x=0.00-0.80,w=0.000-0.332, were studied by powder X-ray diffraction, powder neutron diffraction, Mössbauer spectroscopy, and Fe K-, Sr K-, and Pr L_III-edge EXAFS techniques. The diffraction data revealed no indications for ordering of Pr and Sr at the A site, nor for oxygen vacancy ordering at O sites for heavily reduced samples. Mössbauer spectroscopy showed octahedral, square pyramidal, and tetrahedral Fe coordinations with relative amounts closely following the predictions for a binomial distribution of oxygen vacancies. In addition to Fe³⁺ and Fe⁴⁺, also Fe⁵⁺ appears at 77 K for (G-type) antiferromagnetic samples with high average Fe valence. This suggests dynamic 2 Fe⁴⁺↔Fe³⁺+Fe⁵⁺ fluctuations. At 296 K, a mixed valence Fe⁽³⁺ⁿ⁾⁺ component significantly improved the fit of Mössbauer spectra for the most oxidized paramagnetic samples. The qualitative EXAFS study shows that the local environments for Fe, Pr, and Sr strongly depend on x and w. The local Pr- and Sr-site geometries differ significantly from the cubic average structure for Pr_0.50Sr_0.50FeO_2.746.     

Synthesis and Electrochemical Studies of Spinel LiNi1−xMnxVO4

Spinel compound LiNi_1−xMn_xVO₄ (0≤x≤0.4) had been prepared by using the moist chemical method. X-ray diffraction spectra showed that the lattice constant increased with x in the LiNi_1−xMn_xVO₄, XPS spectra indicating that Li1s had a chemical shift towards lesser binding energy, and manganese in LiNi_1−xMn_xVO₄ existing as the mixed valence of Mn²⁺ and Mn³⁺. The electrochemical charge and discharge testing at a current density of 0.1 mA/cm² between the potentials of 4.0 and 3.0 V vs Li/Li⁺ in 1 mol/dm³ LiPF₆/EC+DEC (1:1 by volume) at 25°C showed that LiNi_1−xMn_xVO₄ cell has a better rechargeability, but a lower cell voltage of 4.0 V vs Li/Li⁺ than that without the doping sample, and the capacity and the cycle efficiency of the Li/LiNi_1−xMn_xVO₄ cells increased with x in the LiNi_1−xMn_xVO₄.