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At least 1,639 records · Page 91
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

High-pressure crystal growth and electromagnetic properties of 5d double-perovskite Ca₃OsO₆

Single crystals of the osmium-containing compound Ca₃OsO₆ have been successfully grown under high-pressure conditions, for the first time. The crystal structure of Ca₃OsO₆ atoms being fully ordered at the perovskite B-site. The electromagnetic analysis shows that the crystal exhibits a semiconductor-like behavior below 300 K and undergoes an antiferromagnetic transition at 50 K. - Graphical Abstract: Schematic image of crystal structure of Ca₃OsO₆ as determined by X-ray diffraction, where the gray and black octahedrons are occupied by Ca and Os, respectively. Top inset reveals an optic image of a typical Ca₃OsO₆ single crystal. Highlights: • Single crystals of Ca₃OsO₆ have been successfully grown under high-pressure. • Ca₃OsO₆ crystalizes into an ordered double-perovskite structure. • The Ca₃OsO₆ undergoes an antiferromagnetic transition at 50 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

New rock salt-related oxides Li{sub 3}M{sub 2}RuO{sub 6} (M=Co, Ni): Synthesis, structure, magnetism and electrochemistry

We describe the synthesis, crystal structure, magnetic and electrochemical characterization of new rock salt-related oxides of formula, Li{sub 3}M{sub 2}RuO{sub 6} (M=Co, Ni). The M=Co oxide adopts the LiCoO{sub 2} (R-3m) structure, where sheets of LiO{sub 6} and (Co{sub 2}/Ru)O{sub 6} octahedra are alternately stacked along the c-direction. The M=Ni oxide also adopts a similar layered structure related to Li{sub 2}TiO{sub 3}, where partial mixing of Li and Ni/Ru atoms lowers the symmetry to monoclinic (C2/c). Magnetic susceptibility measurements reveal that in Li{sub 3}Co{sub 2}RuO{sub 6}, the oxidation states of transition metal ions are Co{sup 3+} (S=0), Co{sup 2+} (S=1/2) and Ru{sup 4+} (S=1), all of them in low-spin configuration and at 10 K, the material orders antiferromagnetically. Analogous Li{sub 3}Ni{sub 2}RuO{sub 6} presents a ferrimagnetic behavior with a Curie temperature of 100 K. The differences in the magnetic behavior have been explained in terms of differences in the crystal structure. Electrochemical studies correlate well with both magnetic properties and crystal structure. Li-transition metal intermixing may be at the origin of the more impeded oxidation of Li{sub 3}Ni{sub 2}RuO{sub 6} when compared to Li{sub 3}Co{sub 2}RuO{sub 6}. Interestingly high first charge capacities (between ca. 160 and 180 mAh g{sup −1}) corresponding to ca. 2/3 of theoretical capacity are reached albeit, in both cases, capacity retention and cyclability are not satisfactory enough to consider these materials as alternatives to LiCoO{sub 2}. - Graphical abstract: Two new rock salt related oxides of formula, Li{sub 3}M{sub 2}RuO{sub 6}, (M=Co, Ni) have been prepared. The M=Co oxide adopts the LiCoO{sub 2} (R-3m) structure and the M=Ni oxide adopts a similar layered structure related to Li{sub 2}TiO{sub 3,} monoclinic (C2/c), with partial mixing of Li and Ni/Ru atoms. For Li{sub 3}Co{sub 2}RuO{sub 6}, oxidation state for Ru is 4+ and antiferromagnetic (AFM) order is found below 10 K while for the analogous Li{sub 3}Ni{sub 2}RuO{sub 6} , Ru oxidation state is 5+ and a ferrimagnetic (FM) behavior with a Curie temperature of 100 K is found. Electrochemical studies correlate well with both magnetic properties and crystal structure. - Highlights: • New Ruthenium rock salt-related oxides of formula, Li{sub 3}M{sub 2}RuO{sub 6} (M=Co, Ni) were studied. • Structurally different: rhombohedral α-NaFeO{sub 2}-type (Co) and monoclinic Li{sub 2}TiO{sub 3}-type (Ni) • Magnetic behavior is different: the Co sample is AFM while the Ni one is ferrimagnetic. • Ruthenium oxidation states are different: 4+ in the Co sample and 5+ in the Ni one. • Electrochemical studies correlate well with magnetic properties and crystal structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Crystal structure and magnetic properties of the Ba{sub 3}TeCo{sub 3}P{sub 2}O{sub 14}, Pb{sub 3}TeCo{sub 3}P{sub 2}O{sub 14}, and Pb{sub 3}TeCo{sub 3}V{sub 2}O{sub 14} langasites

We report the structural and magnetic characterizations of Ba{sub 3}TeCo{sub 3}P{sub 2}O{sub 14}, Pb{sub 3}TeCo{sub 3}P{sub 2}O{sub 14}, and Pb{sub 3}TeCo{sub 3}V{sub 2}O{sub 14}, compounds that are based on the mineral dugganite, which is isostructural to langasites. The magnetic part of the structure consists of layers of Co{sup 2+} triangles. Nuclear and magnetic structures were determined through a co-refinement of synchrotron and neutron powder diffraction data. In contrast to the undistorted P321 langasite structure of Ba{sub 3}TeCo{sub 3}P{sub 2}O{sub 14}, a complex structural distortion yielding a large supercell is found for both Pb{sub 3}TeCo{sub 3}P{sub 2}O{sub 14} and Pb{sub 3}TeCo{sub 3}V{sub 2}O{sub 14}. Comparison of the three compounds studied along with the zinc analog Pb{sub 3}TeZn{sub 3}P{sub 2}O{sub 14}, also characterized here, suggests that the distortion is driven by Pb{sup 2+} lone pairs; as such, the Pb compounds crystallize in a pyroelectric space group, P2. Magnetic susceptibility, magnetization, and heat capacity measurements were performed to characterize the magnetic behavior. All three compounds become antiferromagnetic with Néel temperatures T{sub N}≈21 K (Ba{sub 3}TeCo{sub 3}P{sub 2}O{sub 14}), ≈13 K (Pb{sub 3}TeCo{sub 3}P{sub 2}O{sub 14}), and ≈8 K (Pb{sub 3}TeCo{sub 3}V{sub 2}O{sub 14}), and they exhibit magnetic transitions at high applied magnetic fields, suggesting intrinsically complex magnetic behavior for tetrahedrally coordinated d{sup 7} Co{sup 2+} in this structure type. - Graphical abstract: Ba{sub 3}TeCo{sub 3}P{sub 2}O{sub 14}, Pb{sub 3}TeCo{sub 3}P{sub 2}O{sub 14} and Pb{sub 3}TeCo{sub 3}V{sub 2}O{sub 14} exhibit a triangles-of-triangles arrangement of the magnetic cations. Despite the Pb-induced crystallographic distortion, all of these materials exhibit competing antiferromagnetic and ferromagnetic interactions that lead to complex high field magnetism. - Highlights: • Nuclear and magnetic structures of Ba{sub 3}TeCo{sub 3}P{sub 2}O{sub 14}, Pb{sub 3}TeCo{sub 3}P{sub 2}O{sub 14} and Pb{sub 3}TeCo{sub 3}V{sub 2}O{sub 14}. • Structural characterization shows complex Pb-induced distortion. • Distortion puts Pb-compounds into space group that allows potential multiferroicity. • Magnetic characterization shows competing magnetic interactions. • Triangles of triangles motif results in complex high-field magnetic behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Two new coordination polymers constructed by naphthalene-1,4-dicarboxylic acid and 2,4-diamino-6-methyl-triazine

Two new transition metal coordination complexes, ([MnO(nda)](H{sub 2}dmt)(H{sub 2}O)){sub n} (1), [Ag{sub 5}(nda){sub 2.5}(dmt)]{sub n} (2), (H{sub 2}nda=naphthalene-1,4-dicarboxylic acid, dmt=2,4-diamine-6-methyl-1,3,5-triazine) have been hydrothermally synthesized by the reactions of H{sub 2}nda and dmt with the homologous MnCl{sub 2}·4H{sub 2}O and AgNO{sub 3}, respectively, and characterized by single-crystal X-ray diffraction, IR spectra, elemental analysis, thermogravimetric analysis (TGA). The compound 1 exhibits a 3D network comprising 1D metal chain (MnO(CO{sub 2}){sub 2}){sub n} connected by the ligand nda{sup 2−}, featuring a four-connected uninodal diamond -like topology. In compound 2, it is firstly observed that decanuclear silver units as secondary building units to construct 3D network by the ligands dmt and nda{sup 2−}, with a rare 2-nodal (3,8)-connected tfz-d topology ((4{sup 3}){sub 2}(4{sup 6}.6{sup 18}.8{sup 4})). The interactions within each Mn(II)—Mn(II) pair of compound 1 are antiferromagnetic (g=2.07, J=−1.42(1) cm{sup −1}, zj′=−0.73(2) cm{sup −1}). In addition, compound 2 exhibits photoluminescent property at about 472 nm (λ{sub ex}=394 nm). - Graphical abstract: Two new transition metal coordination complexes 1–2 have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, IR spectra, elemental analysis thermogravimetric analysis (TGA). Highlights: • The compound 1 exhibits a 3D network with four-connected uninodal diamond-like topology. • The first 3D network of 2 with a rare tfz-d topology consists of decanuclear silver clusters as secondary building units. • The magnetic measurement indicates the compound 1 shows antiferromagnetic interactions. • The photoluminescent property of 2 has been measured.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Crystal and magnetic structure of (1−x)BiFeO{sub 3}–xSrTiO{sub 3} (x=0.2, 0.3, 0.4 and 0.8)

The effect of doping SrTiO{sub 3} into BiFeO{sub 3} on the magnetic and crystal structure has been explored using powder neutron diffraction for (1−x)BiFeO{sub 3}–xSrTiO{sub 3} where x=0.2, 0.3, 0.4, 0.6 and 0.8. While the data are not sensitive to the cycloidal component of the magnetic ordering, the evolution of the collinear antiferromagnetic moment of the G-type antiferromagnetic component with T and x has been explored, as have structural parameters. It is found that for x≤0.4 pure phase samples form in the R3c cell, and for x=0.8 a non-magnetic Pm3{sup ¯}m phase is obtained. The x=0.6 sample gives a mixed phase. Through the R3c phase the magnetic structure does not change appreciably apart from the reduction of magnetic moment magnitude with the increasing T and/or x. - Graphical abstract: A simple phase diagram for (1−x)BiFeO{sub 3}–xSrTiO{sub 3} , where hexagons indicate the rhombohedral R3c phase and boxes the cubic phase. Filled symbols indicate magnetic ordering. The black arrow indicates T{sub N} for BiFeO{sub 3}. Display Omitted - Highlights: • We have established part of the phase diagram for doping SrTiO{sub 3} into BiFeO{sub 3}. • (1−x)BiFeO{sub 3}–xSrTiO{sub 3} is isostructural with BiFeO{sub 3} up to x<0.4, and cubic for x>0.85. • We have examined the evolution of ordered magnetic moment with T and x.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Structural and magnetic properties of quasi-one-dimensional doped LiCuVO{sub 4}

The Neutron diffraction, X-ray photoemission and Magnetic properties of Zn, Co and Mn-doped LiCuVO{sub 4} were investigated. Both with Zn and Co doping the antiferromagnetic correlation increase. On the other hand Mn-doping induces the short range ferromagnetic ordering. Neutron diffraction study does not show any phase transition down to 5 K i.e., there is no indication of long range magnetic ordering. Neutron diffraction study also indicates that with Zn, Co and Mn doping the V–O lengths are changed. Maximum change in the V–O distances is observed for Mn-doped sample. On the other hand, X-ray photoemission spectroscopic data indicates Mn doping converts some Cu{sup 2+} ions into Cu{sup 3+} ions. - Graphical abstract: LiCuVO{sub 4} is a quasi-one-dimensional spin magnet. It shows antiferromagnetic ordering. It is observed when Mn is doped in the Cu site of LiCuVO{sub 4} a short range ferromagnetic ordering occurs. - Highlights: • LiCuVO{sub 4} is an one-dimensional spin chain system. • Mn ion is doped in Cu site to induce ferromagnetism. • Doping of Mn ion changes the Cu–O–Cu bond angle which in effect induces ferromagnetism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Synthesis, crystal structure and magnetic properties of Li{sub 2}InMo{sub 3}O{sub 8}: A novel reduced molybdenum oxide containing magnetic Mo{sub 3} clusters

Powder samples and single crystals of Li{sub 2}InMo{sub 3}O{sub 8} were obtained by solid state reaction. The structure was determined by single-crystal X-ray diffraction (771 independent reflections for 33 refinable, R1=0.0158 and wR2=0.0354). Li{sub 2}InMo{sub 3}O{sub 8} is isomorphous with Li{sub 2}SnMo{sub 3}O{sub 8} and crystallizes in the hexagonal space group P6{sub 3}mc with unit-cell parameters a=5.7931(2) Å, c=10.4681(4) Å and Z=2. The crystal structure consists of distorted hexagonal-close-packed oxygen layers with stacking sequence abac along [0 0 1] and that are held together by alternating lithium–indium and molybdenum layers. The Li{sup +} and In{sup 3+} ions occupy, respectively, tetrahedral and octahedral sites in the ratio 2:1. The Mo atoms occupy octahedral sites and form strongly bonded triangular clusters involving three MoO{sub 6} octahedra that are each shared along two edges, constituting a Mo{sub 3}O{sub 13} unit. The variations of the Mo–Mo and Mo–O bond lengths according to the number of electrons per Mo{sub 3} cluster are discussed. The trivalent oxidation state of the indium leads to one unpaired electron per Mo{sub 3} and thus gives rise to a paramagnetic spin behavior with an effective magnetic moment of 1.5 μ{sub B} per Mo{sub 3} cluster. The magnetic susceptibility vs. temperature curve also shows a maximum at 25 K arising probably from an antiferromagnetic ordering between the Mo{sub 3} clusters. - Graphical abstract: We present here the synthesis, the crystal structure, and the magnetic properties of the new quaternary compound Li{sub 2}InMo{sub 3}O{sub 8} containing magnetic Mo{sub 3}O{sub 13} units with one unpaired electron. - Highlights: • The new quaternary reduced molybdenum oxide containing Mo{sub 3} clusters, Li{sub 2}InMo{sub 3}O{sub 8}, was synthesized by solid state reaction. • Single-crystal X-ray study. • One unpaired electron per Mo{sub 3} cluster leading to a paramagnetic spin behavior with an effective magnetic moment of 1.5 μ{sub B} per Mo{sub 3} cluster. • Magnetic susceptibility measurements show a maximum at 25 K arising probably from an antiferromagnetic ordering between the Mo{sub 3} clusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Temperature evolution of nickel sulphide phases from thiourea complex and their exchange bias effect

Considering the very complex phase diagram of nickel sulphide, it is quite challenging to stabilize pure phases from a single precursor. Here, we obtain nanoparticles of various phases of nickel sulphide by decomposing nickel–thiourea complex at different temperatures. The first phase in the evolution is the one with the maximum sulphur content, namely, NiS{sub 2} nanoparticles obtained at 400 °C. As the temperature is increased, nanoparticles of phases with lesser sulphur content, NiS (600 °C) and Ni{sub 3}S{sub 2} (800 °C) are formed. NiS{sub 2} nanoparticles exhibit weak ferromagnetic transition at 30 K and show a large exchange bias at 2 K. NiS nanoparticles are antiferromagnetic and show relatively smaller exchange bias effect. On the other hand, Ni{sub 3}S{sub 2} nanoparticles exhibit very weak temperature dependent magnetization. Electrical measurements show that both NiS{sub 2} and NiS are semiconductors whereas Ni{sub 3}S{sub 2} is a metal. - Graphical abstract: Pure phases of NiS{sub 2}, NiS and Ni{sub 3}S{sub 2} have been obtained by thermal decomposition of nickel–thiourea complex wherein, NiS{sub 2} nanoparticles exhibit remarkable exchange bias effect at 2 K. - Highlights: • NiS{sub 2}, NiS and Ni{sub 3}S{sub 2} nanoparticles are obtained by thermal decomposition of nickel–thiourea complex at different temperatures. • As the temperature is increased, nickel sulphide phase with lesser sulphur content is obtained. • NiS{sub 2} nanoparticles show good exchange bias property which can be explained by antiferromagnetic core and ferromagnetic shell model. • NiS{sub 2} and NiS are semiconducting while Ni{sub 3}S{sub 2} shows metallic behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Rare-earth transition-metal gallium chalcogenides RE{sub 3}MGaCh{sub 7} (M=Fe, Co, Ni; Ch=S, Se)

Six series of quaternary rare-earth transition-metal chalcogenides RE{sub 3}MGaCh{sub 7} (M=Fe, Co, Ni; Ch=S, Se), comprising 33 compounds in total, have been prepared by reactions of the elements at 1050 °C (for the sulphides) or 900 °C (for the selenides). They adopt noncentrosymmetric hexagonal structures (ordered Ce{sub 3}Al{sub 1.67}S{sub 7}-type, space group P6{sub 3}, Z=2) with cell parameters in the ranges of a=9.5–10.2 Å and c=6.0–6.1 Å for the sulphides and a=10.0–10.5 Å and c=6.3–6.4 Å for the selenides as refined from powder X-ray diffraction data. Single-crystal structures were determined for five members of the sulphide series RE{sub 3}FeGaS{sub 7} (RE=La, Pr, Tb) and RE{sub 3}CoGaS{sub 7} (RE=La, Tb). The highly anisotropic crystal structures consist of one-dimensional chains of M-centred face-sharing octahedra and stacks of Ga-centred tetrahedra all pointing in the same direction. Magnetic measurements on the sulphides reveal paramagnetic behaviour in some cases and long-range antiferromagnetic behaviour with low Néel temperatures (15 K or lower) in others. Ga L-edge XANES spectra support the presence of highly cationic Ga tetrahedral centres with a tendency towards more covalent Ga–Ch character on proceeding from the sulphides to the selenides. Band structure calculations on La{sub 3}FeGaS{sub 7} indicate that the electronic structure is dominated by Fe 3d-based states near the Fermi level. - Graphical abstract: The series of chalcogenides RE{sub 3}MGaS{sub 7}, which form for a wide range of rare-earth and transition metals (M=Fe, Co, Ni), adopt highly anisotropic structures containing chains of M-centred octahedra and stacks of Ga-centred tetrahedra. Display Omitted - Highlights: • Six series (comprising 33 compounds) of chalcogenides RE{sub 3}MGaCh{sub 7} were prepared. • They adopt noncentrosymmetric hexagonal structures with high anisotropy. • Most compounds are paramagnetic; some show antiferromagnetic ordering. • Ga L-edge XANES confirms presence of cationic Ga species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Structure and properties of α-NaFeO{sub 2}-type ternary sodium iridates

The synthesis, structure, and elementary magnetic and electronic properties are reported for layered compounds of the type Na{sub 3−x}MIr{sub 2}O{sub 6} and Na{sub 3−x}M{sub 2}IrO{sub 6}, where M is a transition metal from the 3d series (M=Zn, Cu, Ni, Co, Fe and Mn). The rhombohedral structures, in space group R−3m, were determined by refinement of neutron and synchrotron powder diffraction data. No clear evidence for long range 2:1 or 1:2 honeycomb-like M/Ir ordering was found in the neutron powder diffraction patterns except in the case of M=Zn, and thus in general the compounds are best designated as sodium deficient α-NaFeO{sub 2}-type phases with formulas Na{sub 1−x}M{sub 1/3}Ir{sub 2/3}O{sub 2} or Na{sub 1−x}M{sub 2/3}Ir{sub 1/3}O{sub 2}. Synchrotron powder diffraction patterns indicate that several of the compounds likely have honeycomb in-plane metal–iridium ordering with disordered stacking of the layers. All the compounds are sodium deficient under our synthetic conditions and are black and insulating. Weiss constants derived from magnetic susceptibility measurements indicate that Na{sub 0.62}Mn{sub 0.61}Ir{sub 0.39}O{sub 2}, Na{sub 0.80}Fe{sub 2/3}Ir{sub 1/3}O{sub 2}, Na{sub 0.92}Ni{sub 1/3}Ir{sub 2/3}O{sub 2}, Na{sub 0.86}Cu{sub 1/3}Ir{sub 2/3}O{sub 2}, and Na{sub 0.89}Zn{sub 1/3}Ir{sub 2/3}O{sub 2} display dominant antiferromagnetic interactions. For Na{sub 0.90}Co{sub 1/3}Ir{sub 2/3}O{sub 2} the dominant magnetic interactions at low temperature are ferromagnetic while at high temperatures they are antiferromagnetic; there is also a change in the effective moment. Low temperature specific heat measurements (to 2 K) on Na{sub 0.92}Ni{sub 1/3}Ir{sub 2/3}O{sub 2} indicate the presence of a broad magnetic ordering transition. X-ray absorption spectroscopy shows that iridium is at or close to the 4+ oxidation state in all compounds. {sup 23}Na nuclear magnetic resonance measurements comparing Na{sub 2}IrO{sub 3} to Na{sub 0.92}Ni{sub 1/3}Ir{sub 2/3}O{sub 2} and Na{sub 0.89}Zn{sub 1/3}Ir{sub 2/3}O{sub 2} provide strong indications that the electron spins are short-range ordered in the latter two materials. Na{sub 0.62}Mn{sub 0.61}Ir{sub 0.39}O{sub 2}, Na{sub 0.80}Fe{sub 2/3}Ir{sub 1/3}O{sub 2}, Na{sub 0.90}Co{sub 1/3}Ir{sub 2/3}O{sub 2}, Na{sub 0.92}Ni{sub 1/3}Ir{sub 2/3}O{sub 2}, Na{sub 0.86}Cu{sub 1/3}Ir{sub 2/3}O{sub 2} and Na{sub 0.89}Zn{sub 1/3}Ir{sub 2/3}O{sub 2} are spin glasses. (CSD-numbers: Na{sub 0.62}Mn{sub 0.61}Ir{sub 0.39}O{sub 2}: 426657, Na{sub 0.80}Fe{sub 2/3}Ir{sub 1/3}O{sub 2}: 426659, Na{sub 0.90}Co{sub 1/3}Ir{sub 2/3}O{sub 2}: 426658, Na{sub 0.92}Ni{sub 1/3}Ir{sub 2/3}O{sub 2}: 426656, Na{sub 0.86}Cu{sub 1/3}Ir{sub 2/3}O{sub 2}: 426655, and Na{sub 2.8}ZnIr{sub 2}O{sub 6}: 426660.) - Graphical abstract: Diffraction patterns of Na{sub 0.92}Ni{sub 1/3}Ir{sub 2/3}O{sub 2}, Na{sub 0.86}Cu{sub 1/3}Ir{sub 2/3}O{sub 2} and Na{sub 0.89}Zn{sub 1/3}Ir{sub 2/3}O{sub 2}: neutron diffraction patterns in the main panel and synchrotron diffraction in the insets. The patterns show a small amount of ordering in the transition metal iridium layer. Display Omitted - Highlights: • We report six ternary sodium iridates with the α-NaFeO{sub 2} structure. • Compounds Na{sub 1−x}M{sub 1/3}Ir{sub 2/3}O{sub 2}, M=Co, Ni, Cu, Zn and Na{sub 1−x}M{sub 2/3}Ir{sub 1/3}O{sub 2}, M=Mn, Fe. • Rietveld refinement of powder neutron diffraction data. • All compounds are spin glasses. • NMR comparison to Na{sub 2}IrO{sub 3}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Crystal structure, oxidation state and magnetism of Sr{sub x}La{sub 2−x}Cu{sub 0.5}Ru{sub 0.5}O{sub 4} (x=1, 1.5)

Sr{sub x}La{sub 2−x}Cu{sub 0.5}Ru{sub 0.5}O{sub 4} (x=1, 1.5) oxides with K{sub 2}NiF{sub 4}-type structure were prepared by solid state reaction and characterized by powder X-ray diffraction, X-ray photoelectron spectroscopy, magnetic and electrical resistivity measurements. The SrLaCu{sub 0.5}Ru{sub 0.5}O{sub 4} phase was obtained for the first time with a negligible amount of impurities. The octahedral Cu/RuO{sub 6} units are more elongated in SrLaCu{sub 0.5}Ru{sub 0.5}O{sub 4} than in Sr{sub 1.5}La{sub 0.5}Cu{sub 0.5}Ru{sub 0.5}O{sub 4} indicating a greater extent of static Jahn–Teller distortion. XPS suggests that mixed ion pairs Ru{sup 5+}/Ru{sup 4+}↔Cu{sup +}/Cu{sup 2+} are present in SrLaCu{sub 0.5}Ru{sub 0.5}O{sub 4}, while Ru remains as Ru{sup 5+} and Cu as Cu{sup 2+} in Sr{sub 1.5}La{sub 0.5}Cu{sub 0.5}Ru{sub 0.5}O{sub 4}. Both samples show spin-glass behavior, which can be explained by competition between ferromagnetic and antiferromagnetic superexchange interactions. The negative Weiss temperature estimated for SrLaCu{sub 0.5}Ru{sub 0.5}O{sub 4}, −318 K, is significantly lower than −11.5 K deduced for Sr{sub 1.5}La{sub 0.5}Cu{sub 0.5}Ru{sub 0.5}O{sub 4} which may be related to the higher static Jahn–Teller distortion in the former oxide. -- Graphical abstract: SrLaCu{sub 0.5}Ru{sub 0.5}O{sub 4} with K{sub 2}NiF{sub 4}-type structure show a larger static Jahn–Teller distortion than Sr{sub 1.5}La{sub 0.5}Cu{sub 0.5}Ru{sub 0.5}O{sub 4}, which may be related to stronger antiferromagnetic superexchange interactions. Highlights: • SrLaCu{sub 0.5}Ru{sub 0.5}O{sub 4} (I) larger Jahn–Teller (J–T) distortion than Sr{sub 1.5}La{sub 0.5}Cu{sub 0.5}Ru{sub 0.5}O{sub 4} (II). • Octahedral Cu/RuO{sub 6} units are more elongated in I than in II. • Mixed ion pairs Ru{sup 5+}/Ru{sup 4+}↔Cu{sup +}/Cu{sup 2+} are present in I, while Ru remains as Ru{sup 5+} and Cu as Cu{sup 2+} in II. • Negative Weiss temperature of I significantly lower, consistent with higher J–T distortion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Synthesis, characterization and magnetic properties of a manganese (II) silicate containing frustrated S=5/2 zig–zag ladders

The hydrothermal synthesis, structural characterization and magnetic properties of a manganese silicate with ideal formula of NaMn{sub 2}Si{sub 3}O{sub 8}(OH) is reported. This compound is a synthetic analog to the naturally occurring mineral Serandite. The crystal structure comprises MnO{sub 6} octahedra and SiO{sub 4} tetrahedra. The MnO{sub 6} share four edges with neighboring octahedra forming double chains. These chains are connected by silicate chains Si{sub 3}O{sub 8}(OH) resulting in an open framework structure with six-member ring channels where sodium ions are located. From the magnetic point of view, the intra-chain exchange between neighboring S=5/2 manganese ions is weak, partly due to the distortion observed in the octahedra, but also due to the frustrated topology of the chain. A successful fitting of the magnetic susceptibility was obtained by considering a double chain numerical model with Monte Carlo derived empirical parameters. -- Graphical abstract: A manganese silicate prepared hydrothermally with formula NaMn{sub 2}Si{sub 3}O{sub 8}(OH) possessing the structure of the mineral Serandite contains doubled chains of edge-sharing MnO{sub 6} octahedra. The magnetic susceptibility was measured and shows an antiferromagnetic behavior. Highlights: • Characterization of a synthetic analog to the mineral Serandite: NaMn{sub 2}Si{sub 3}O{sub 8}(OH). • Fitting of the magnetic susceptibility considering a classical regular chain. • Weak metal–oxygen–metal super-exchange interactions; antiferromagnetic in nature. • Elevated degree of frustration along the chain, without sign of interchain ordering.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Structural, electrochemical and magnetic characterization of the layered-type PrBa{sub 0.5}Sr{sub 0.5}Co{sub 2}O{sub 5+δ} perovskite

Structural, electrical and magnetic properties of the layered cobaltite PrBa{sub 0.5}Sr{sub 0.5}Co{sub 2}O{sub 5+δ} have been investigated by means of neutron diffraction, electron diffraction, thermogravimetric analysis and SQUID magnetometry. Rietveld analysis of neutron diffraction data shows the ordered distribution of oxygen vacancies in [PrO{sub δ}] planes which doubles the lattice parameters from the simple perovskite cell parameter as a≈2a{sub p} and c≈2a{sub p} (a{sub p} is the cell parameter of the simple Perovskite) yielding tetragonal symmetry in the P4/mmm space group. On heating, above 573 K in air, structural rearrangement takes place and the structure can be defined as a≈a{sub p} and c≈2a{sub p} in the same space group. Oxygen occupancies have been determined as a function of temperature from neutron diffraction results. Initially (≥373 K), oxygen occupancy was increased and then decreased with increasing temperature. It was found that at 973 K the total oxygen loss is calculated about 0.265 oxygen/formula unit. Oxygen vacancy ordering was observed below 573 K, and the oxygen occupancy decreases as cell volume increases with increasing temperature. Area specific resistance (ASR) measurements show a resistance of 0.153 Ωcm{sup 2} and 0.286 Ωcm{sup 2} at 973 K and 923 K, respectively. On cooling, paramagnetic to ferromagnetic and an incomplete ferromagnetic to antiferromagnetic transition takes place. Different behaviours in field cooled and zero-field-cooled measurements leads to a coexistence of ferromagnetic and antiferromagnetic order. - Graphical abstract: Structural phase changes in PrBa{sub 0.5}Sr{sub 0.5}Co{sub 2}O{sub 5+δ} at elevated temperatures determined by neutron powder diffraction. Depending on oxygen occupancy it form different phases at different temperatures. This pictures show the schematic 3D diagram of PrBa{sub 0.5}Sr{sub 0.5}Co{sub 2}O{sub 5+δ} at 295 K (a), 373 K (b) and 573 K (c). Co atoms are inside the octahedra/pyramid. Ba and Sr occupy the same site. Oxygens are in the corner of polyhedra. - Highlights: • Structural phase changes at high temperatures. • Ordered distribution of oxygen vacancies below 573 K. • Double Perovskite type structure below 373 K in the P4/mmm space group. • Structural changes have direct correlation with conductivity. • Low area specific resistance at 973 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Magnetic properties of pseudo-ideal cubic La{sub 0.6−x}Ca{sub x}Ba{sub 0.4}CoO{sub 3} with hole doping

The La{sub 0.6−x}Ca{sub x}Ba{sub 0.4}CoO{sub 3} (x=0.03, 0.04, 0.05, 0.075, 0.1 and 0.15) compounds are synthesized. The cubic La{sub 0.6}Ba{sub 0.4}CoO{sub 3} has the strongest ferromagnetic (FM) double exchange interaction among all the La–Ba–Co–O compounds due to the straight Co–O–Co bond. The variation of the lattice parameter versus the calcium content exhibits a non-linear dependence and has the lowest value at x=0.05. In La{sub 0.6−x}Ca{sub x}Ba{sub 0.4}CoO{sub 3} compounds with x≤0.05, the magnetic frustration is observed below about 190 K, and the substitution of Ca{sup 2+} for La{sup 3+} enhances the FM interaction due to the increasing double exchange through Co{sup 3+}–O{sup 2−}–Co{sup 4+} bond. The analysis based on the measured magnetization at 50 kOe and the calculated value indicates that Co{sup 3+} ions are almost equally distributed at the low spin state and the intermediate spin state, and the Co{sup 4+} ions are at the low spin state. La{sub 0.55}Ca{sub 0.05}Ba{sub 0.4}CoO{sub 3} has the lowest coercivity. As the composition deviates from x=0.05, the coercivity is enhanced. For the samples with θ{sub CW}, the substitution of Ca{sup 2+} ions enhances the antiferromagnetic (AFM) interaction, and it is strong enough to make the long range AFM interaction appear. The percentage of the FM domains is calculated, and it decreases very quickly with the Ca{sup 2+} content x≥0.05. The sample with x=0.15 is mostly composed of AFM domains, and its AFM–FM transition temperature is 120 K. Another FM interaction with a low magnetic moment at the low temperature is also observed. - Graphical abstract: The thermal magnetization at 200 Oe at the ZFC and the FC states. - Highlights: • We studied the hole doping on the magnetic properties of La{sub 0.6−x}Ca{sub x}Ba{sub 0.4}CoO{sub 3}. • With x≤0.05, Ca{sup 2+} enhances the ferromagnetic interaction. • With θ{sub CW}, Ca{sup 2+} induces long range antiferromagnetic interaction. x=0.15 is mostly AFM. • Co{sup 3+} ions are equally distributed at LS and IS state, and Co{sup 4+} are at LS state. • We analyzed the development of the magnetic interaction with the doping Ca{sup 2+}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Different dimensional coordination polymers with 4,4'-oxybis(benzoate): Syntheses, structures and properties

Five transition-metal coordination polymers, namely, [Zn{sub 7}Cl{sub 6}(oba){sub 4}]{sub n} (1), [Cd{sub 7}Cl{sub 6}(oba){sub 4}]{sub n} (2), [Zn(oba)(H{sub 2}O)]{sub n} (3), [Ag{sub 2}(oba)]{sub n} (4) and [Co(oba)(H{sub 2}O){sub 2}]{sub n} (5) (H{sub 2}oba=4,4′-oxydibenzoic acid), have been achieved under hydrothermal conditions and structurally characterized by IR, elemental analyses, X-ray single-crystal diffraction and TGA. The X-ray single-crystal diffraction reveals that compounds 1 and 2 are isomorphism, featuring pillared-layer 3D motifs, in which the 2D inorganic layers (Zn{sub 6}Cl{sub 7}){sub n} (or (Cd{sub 6}Cl{sub 7}){sub n}) are connected by oba{sup 2−} pillars. Compound 3 exhibits 1D stair-like chain and extends to a 3D network by two different interchain O–H–O hydrogen bonding interactions while compound 4 features wave chains and stretches to 2D layer by interchain Ag–O weak contacts. Compound 5 shows 2D network in which Co-chains are pillared by oba{sup 2−} ligand and then forms a 3D network by four different O–H–O hydrogen bonding interactions. Furthermore, 1–4 exhibit luminescent properties at a solid state and 5 shows antiferromagnetic behavior. - Graphical abstract: Five new transition-metal coordination complexes 1–5 have been synthesized and characterized by single-crystal X-ray diffractions, IR spectra, elemental analyses, thermogravimetric analyses (TGA), photoluminescent spectra and magnetic measurement. - Highlights: • Compound 1 exhibits a pillared-layer 3D network. • The photoluminescent properties of 1–4 have been measured. • Compound 5 exhibits antiferromagnetic behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Magnetic structures of β{sub I}-Li{sub 2}CoSiO{sub 4} and γ{sub 0}-Li{sub 2}MnSiO{sub 4}: Crystal structure type vs. magnetic topology

The magnetic structure and properties of the candidate lithium-ion battery cathode materials Pbn2{sub 1}(≡Pna2{sub 1}) Li{sub 2}CoSiO{sub 4} and P2{sub 1}/n Li{sub 2}MnSiO{sub 4} have been studied experimentally using low-temperature neutron powder diffraction and magnetometry. Both materials undergo long-range antiferromagnetic ordering, at 14 K and 12 K respectively, due to super–super-exchange mediated by bridging silicate groups. Despite having different crystal structures (wurtzite- vs. “dipolar”-type), Li{sub 2}CoSiO{sub 4} and Li{sub 2}MnSiO{sub 4} have the same topology in terms of magnetic interactions, and adopt collinear magnetic structures of the same type with the propagation vectors (0, 1/2, 1/2) and (1/2, 0, 1/2), respectively. The magnetic moments in the two materials are aligned in parallel and obliquely to the distorted closed-packed layers of oxygen atoms. The experimentally observed values of the ordered magnetic moments, 2.9 μ{sub B} and 4.6 μ{sub B}, are close to those expected for d{sup 7} Co{sup 2+} and d{sup 5} Mn{sup 2+}, respectively. - Graphical abstract: Despite the different crystal structures β{sub I}-Li{sub 2}CoSiO{sub 4} and γ{sub 0}-Li{sub 2}MnSiO{sub 4} have similar magnetic topology and as a result adopt magnetic structure of the same type. - Highlights: • Magnetic structures of Li{sub 2}CoSiO{sub 4} and Li{sub 2}MnSiO{sub 4} were studied for the first time. • Both materials antiferromagnetically order around 12–14 K. • Despite different crystal structure magnetic structures are of the same type. • The fact is attributed to similar topology of magnetic interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Spin glass behavior in the Dy{sub 3-x}Y{sub x}TaO{sub 7} (0≤x≤1) system

Several x-compositions of the polycrystalline Dy{sub 3−x}Y{sub x}TaO{sub 7} system, crystallizing in the weberite-type structure, were synthesized and structurally characterized using Rietveld refinements based on X-ray diffraction data. In previous magnetic characterization of Dy{sub 3}TaO{sub 7} (x=0), with the same crystal structure, an antiferromagnetic transition at T=2.3 K has been assigned to this compound. On the basis of DC and AC magnetic susceptibilities analyses, we show in this work that all compounds in the range of 0≤x≤1.0 exhibit a spin glass behavior. The nature of the spin glass behavior in Dy{sub 3−x}Y{sub x}TaO{sub 7}, can be attributed to the highly frustrated antiferromagnetic interaction of the Dy{sup 3+} sublattice and to the Dy{sup 3+}–Dy{sup 3+} distorted tetrahedra array in the weberite-type structure of this system. By fitting AC susceptibility data, using dynamical scaling theory equations, we conclude that a cluster spin glass is present in Dy{sub 3−x}Y{sub x}TaO{sub 7} in the low temperature range. Depending on the x-composition, T{sub g}∼2.2–3.2 K. In the range 15–300 K the system obeys a Curie–Weiss magnetic behavior. - Graphical abstract: Weberite-type crystal structure of the Dy{sub 3−x}Y{sub x}TaO{sub 7} compounds. In this structure the magnetic sublattice is formed by Dy{sup 3+} cations in an arrangement of distorted tetrahedra at the second-nearest neighbor site; this arrangement suggests geometric frustration that leads to a spin glass behavior. - Highlights: • Spin glass of Dy{sub 3−x}Y{sub x}TaO{sub 7} is associated to highly frustrated AFM interaction. • Quasi-one-dimensional feature of the crystal structure. • Suggest the existence of a cluster spin glass in Dy{sub 3−x}Y{sub x}TaO{sub 7}. • Dy{sub 3−x}Y{sub x}TaO{sub 7} system (x=0.33, 0.66, and 1.0) also display spin glass behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

High-pressure synthesis, crystal structure and magnetic properties of double perovskite oxide Ba{sub 2}CuOsO{sub 6}

A new compositional double perovskite oxide Ba{sub 2}CuOsO{sub 6} was synthesized under high-pressure (6 GPa) and high-temperature (1500 °C) conditions. The polycrystalline Ba{sub 2}CuOsO{sub 6} was characterized by synchrotron X-ray diffraction, thermogravimetric analysis, and magnetic susceptibility, isothermal magnetization, and specific heat measurements. The oxide crystallizes in a double-perovskite structure with an I4/m space group, in which Os(VI) and Cu(II) are ordered in the perovskite B-site. Ba{sub 2}CuOsO{sub 6} is electrically insulating with an activation energy of 0.813(2) eV and shows antiferromagnetic-like characteristics at temperatures of ∼55 K and ∼70 K. The results of the first-principle calculation suggested that the spin–orbit interaction of Os(VI) plays a substantial role in the insulating state. The Jahn–Teller distortion of CuO{sub 6} octahedra influences the magnetic characteristics with regard to possible two-dimensional magnetic correlations. - Graphical abstract: A new compositional double perovskite oxide Ba{sub 2}CuOsO{sub 6} synthesized by a high-pressure (6 GPa) and high-temperature (1500 °C) method. - Highlights: • A new compositional double perovskite oxide Ba{sub 2}CuOsO{sub 6} was synthesized. • Ba{sub 2}CuOsO{sub 6} is electrically insulating and antiferromagnetic below ∼70 K. • The Jahn–Teller distortion of CuO{sub 6} has relevance to possible magnetic anisotropy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗