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Title: Synthesis and structural and magnetic characterization of the frustrated magnetic system La{sub 2}Ni{sub 4/3−x}Co{sub x}Sb{sub 2/3}O{sub 6}

Abstract

We report the synthesis of double perovskites La{sub 2}Ni{sub 4/3−x}Co{sub x}Sb{sub 2/3}O{sub 6} with x=0, 1/3, 2/3 and 1 by a solid state method. Rietveld refinements of X-ray and neutron powder diffraction data show that all samples crystallize in space group P2{sub 1}/n, with almost perfect occupation of the 2d octahedral site with the transition metals, while all Sb{sup 5+} are randomly distributed in a 2c octahedral site. The saturation magnetization in hysteresis loops indicates that the samples are ferrimagnetic throughout all the series. Virgin magnetization curves lie outside hysteresis loops at low temperatures and thermal evolution of H{sub m} – defined as the inflection point of these curves – follows the de Almeida–Thouless dependence for x≠0. This spin glass like behavior below 30 K is also supported by thermal evolution of the coercivity, which follows an exponential law typical of magnetic clusters, not found in the pure Ni{sup 2+} perovskite, x=0 extreme. - Graphical abstract: Display Omitted - Author-Highlights: • We synthesized new double perovskites: La{sub 2}Ni{sub 4/3−x}Co{sub x}SbO{sub 6} (x=1/3, 2/3, 1). • The cations occupying octahedral sites are highly ordered in all samples. • Magnetic transition occurs as a consequence of superexchange paths. • Frustration is foundmore » and attributed to competition between different interactions.« less

Authors:
 [1];  [2];  [3];  [1];  [4]
  1. Laboratorio de Bajas Temperaturas, Centro Atómico Bariloche (CNEA), 8400 Bariloche, Río Negro (Argentina)
  2. (Argentina)
  3. INFIQC-CONICET, Dpto. de Físico-Química, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, X5000HUA Córdoba (Argentina)
  4. (CNEA-UNCuyo) Centro Atómico Bariloche, 8400 Bariloche, Río Negro (Argentina)
Publication Date:
OSTI Identifier:
22274147
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 207; Other Information: Copyright (c) 2013 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANTIMONY IONS; CATIONS; COERCIVE FORCE; FERRIMAGNETISM; HYSTERESIS; INTERACTIONS; MAGNETIZATION; MONOCLINIC LATTICES; NEUTRON DIFFRACTION; NICKEL IONS; PEROVSKITE; SOLIDS; SPACE GROUPS; SPIN GLASS STATE; SYNTHESIS; TRANSITION ELEMENTS; X RADIATION

Citation Formats

Franco, D.G., E-mail: diego.g.franco@cab.cnea.gov.ar, INFIQC-CONICET, Dpto. de Físico-Química, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, X5000HUA Córdoba, Carbonio, R.E., Nieva, G., and Instituto Balseiro. Synthesis and structural and magnetic characterization of the frustrated magnetic system La{sub 2}Ni{sub 4/3−x}Co{sub x}Sb{sub 2/3}O{sub 6}. United States: N. p., 2013. Web. doi:10.1016/J.JSSC.2013.09.011.
Franco, D.G., E-mail: diego.g.franco@cab.cnea.gov.ar, INFIQC-CONICET, Dpto. de Físico-Química, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, X5000HUA Córdoba, Carbonio, R.E., Nieva, G., & Instituto Balseiro. Synthesis and structural and magnetic characterization of the frustrated magnetic system La{sub 2}Ni{sub 4/3−x}Co{sub x}Sb{sub 2/3}O{sub 6}. United States. doi:10.1016/J.JSSC.2013.09.011.
Franco, D.G., E-mail: diego.g.franco@cab.cnea.gov.ar, INFIQC-CONICET, Dpto. de Físico-Química, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, X5000HUA Córdoba, Carbonio, R.E., Nieva, G., and Instituto Balseiro. Fri . "Synthesis and structural and magnetic characterization of the frustrated magnetic system La{sub 2}Ni{sub 4/3−x}Co{sub x}Sb{sub 2/3}O{sub 6}". United States. doi:10.1016/J.JSSC.2013.09.011.
@article{osti_22274147,
title = {Synthesis and structural and magnetic characterization of the frustrated magnetic system La{sub 2}Ni{sub 4/3−x}Co{sub x}Sb{sub 2/3}O{sub 6}},
author = {Franco, D.G., E-mail: diego.g.franco@cab.cnea.gov.ar and INFIQC-CONICET, Dpto. de Físico-Química, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, X5000HUA Córdoba and Carbonio, R.E. and Nieva, G. and Instituto Balseiro},
abstractNote = {We report the synthesis of double perovskites La{sub 2}Ni{sub 4/3−x}Co{sub x}Sb{sub 2/3}O{sub 6} with x=0, 1/3, 2/3 and 1 by a solid state method. Rietveld refinements of X-ray and neutron powder diffraction data show that all samples crystallize in space group P2{sub 1}/n, with almost perfect occupation of the 2d octahedral site with the transition metals, while all Sb{sup 5+} are randomly distributed in a 2c octahedral site. The saturation magnetization in hysteresis loops indicates that the samples are ferrimagnetic throughout all the series. Virgin magnetization curves lie outside hysteresis loops at low temperatures and thermal evolution of H{sub m} – defined as the inflection point of these curves – follows the de Almeida–Thouless dependence for x≠0. This spin glass like behavior below 30 K is also supported by thermal evolution of the coercivity, which follows an exponential law typical of magnetic clusters, not found in the pure Ni{sup 2+} perovskite, x=0 extreme. - Graphical abstract: Display Omitted - Author-Highlights: • We synthesized new double perovskites: La{sub 2}Ni{sub 4/3−x}Co{sub x}SbO{sub 6} (x=1/3, 2/3, 1). • The cations occupying octahedral sites are highly ordered in all samples. • Magnetic transition occurs as a consequence of superexchange paths. • Frustration is found and attributed to competition between different interactions.},
doi = {10.1016/J.JSSC.2013.09.011},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 207,
place = {United States},
year = {Fri Nov 15 00:00:00 EST 2013},
month = {Fri Nov 15 00:00:00 EST 2013}
}
  • The reactions of the cis-dioxorhenium(VII)-catecholate complex [(CH{sub 3}CH{sub 2}){sub 4}N][ReO{sub 2}(O{sub 2}C{sub 6}H{sub 4}){sub 2}] (1) with either monosubstituted organohydrazines (C{sub 6}H{sub 5}NHNH{sub 2}; 4-BrC{sub 6}H{sub 4}NHNH{sub 2}) or 1,1 disubstituted organohydrazines (Ph{sub 2-}NNH{sub 2}) yield the cis-bis(diazenido) core complexes [(CH{sub 3}CH{sub 2}){sub 4}N][Re(NNR){sub 2}(O{sub 2}C{sub 6}H{sub 4}){sub 2}] (5, R = C{sub 6}H{sub 5}; 6, R = 4-BrC{sub 6}H{sub 4}) and the cis-bis(hydrazido) core species [(CH{sub 3}CH{sub 2}){sub 4}N][Re(NNPh{sub 2}){sub 2}(O{sub 2}C36H{sub 4}){sub 2}(O{sub 2}C36H{sub 4}){sub 2}] (7). Elution of 5 in a 3:1 mixture of toluene/methanol on a column of silica gel resulted in cation exchange to givemore » Na[Re(NNPh){sub 2}-(O{sub 2}C{sub 6}H{sub 4}){sub 2}]{center_dot}CH{sub 3}CN (8) as a one-dimensional polymer ([Na(CH{sub 3}CN)]{sup +}[Re(NNPh){sub 2}(O{sub 2}C{sub 6}H{sub 4}){sub 2}]{sup {minus}}){sub 2}. Crystal data for C{sub 32}H{sub 38}N{sub 5}O{sub 4}Re (5): P2{sub 1}/c,a = 14.458(3) {angstrom}, b = 10.436(2) {angstrom}, c = 21.767(4) {angstrom}, {beta} = 107.04(3){degrees}, V = 3140(2) {angstrom}{sup 3}, Z = 4, D {sub calc} = 1.572 g cm{sup {minus}3}; structure solution and refinement based on 3256 reflections with I{sub o} {ge} 3{sigma}(I{sub o}) converged at R = 0.053. Crystal data for C{sub 44}H{sub 48}N{sub 5}O{sub 4}Re (7): P1, a = 11.660(2) {angstrom}, b = 11.864(2) {angstrom}, c = 15.400(2) {angstrom}, {alpha} = 107.12(3){degrees}, {beta} = 94.99(3){degrees}, {gamma} = 97.61(3){degrees}, V = 2000(1) {angstrom}{sup 3}, Z = 2, D{sub calc} = 1.490 g cm{sup {minus}3}; 3702 reflections, R = 0.0534. Crystal data for C{sub 26}H{sub 18}N{sub 5}NaO{sub 4}Re (8): P2/n, a = 5.785(1) {angstrom}, b = 9.670(2) {angstrom}, c = 23.142(5) {angstrom}. {beta} = 90.91(30)degrees, V = 1294.4(7) {angstrom}{sup 3}, Z = 2, D{sub calc} = 1.737 g cm{sup {minus}3}; 1517 reflections, R = 0.049.« less
  • Heteronuclear complexes in the series La[Fe{sub x}Co{sub 1{minus}x}(CN{sub 6})]{center_dot}nH{sub 2}O, with x = 0--1 were prepared. Some complexes consisted of a mixture of hexagonal and orthorhombic phases, due to the presence of different amounts of crystallization water molecules. The lattice constants estimated for the orthorhombic structures increased linearly with increasing Fe content, x. The formation of the perovskite-type oxides by the thermal decomposition of the complexes has been studied by simultaneous thermogravimetric and differential thermal analysis (TG/DTA), X-ray fluorescence (XRF), and X-ray diffraction (XRD). The thermal decomposition of the complexes caused the formation of a single perovskitic phase at differentmore » temperatures, depending on the Fe content. Orthorhombic LaFeO{sub 3} and hexagonal LaCoO{sub 3} were already obtained at about 600 C from the decomposition of the corresponding complexes. For the complexes containing both Fe and Co, the elemental analysis showed that the Fe content was always lower than the prescribed ratios. The single perovskitic phase was formed with increasing temperature as the prescribed ratios of Fe and Co became more similar, the maximum being for x = 0.5; at 1,000 C, a single hexagonal phase was formed for x {le} 0.35, and a single orthorhombic phase was formed for x {ge} 0.44, both being the measured values.« less
  • Trace amounts of H/sub 2/O and limited exposure to air of reaction mixtures of UCl/sub 4/ and 12-crown-4, 15-crown-5, benzo-15-crown-5, 18-crown-6, or dibenzo-18-crown-6 in 1:3 mixtures of CH/sub 3/OH and CH/sub 3/CN resulted in the hydrolysis and oxidation of UCl/sub 4/ to (UO/sub 2/Cl/sub 4/)/sup 2/minus//. In the presence of these crown ethers, it has been possible to isolate intermediate products via crystallization of crown complexes of the (UO/sub 2/Cl/sub 4/)/sup 2/minus// ion, the (UCl/sub 6/)/sup 2/minus// ion, and (UO/sub 2/Cl/sub 2/(OH/sub 2/)/sub 3/). The neutral moiety crystallizes as a hydrogen-bonded crown ether complex; however, crown ether complexation of amore » counterion, either an ammonium ion formed during the oxidation of U(IV) or a Na/sup +/ ion leached from glass reaction vessels, resulted in novel crystalline complexes of the ionic species. ((NH/sub 4/)(15-crown-5)/sub 2/)/sub 2/(UO/sub 2/Cl/sub 4/) /times/ 2CH/sub 3/CN, ((NH/sub 4/)(benzo-15-crown-5)/sub 2/)/sub 2/(UCl/sub 6/) /times/ 4CH/sub 3/CN, and ((NH/sub 4/)(dibenzo-18-crown-6))/sub 2/(UO/sub 2/Cl/sub 4/) /times/ 2CH/sub 3/CN have been structurally characterized by single-crystal X-ray diffraction techniques. The results of all the crystal studies are presented in detail. The ammonium ions interact with the crown ethers via hydrogen-bonding and electrostatic interactions. 15-Crown-5 and benzo-15-crown-5 form 2:1 sandwich cations, allowing no H/sub 4/N/sup +//hor ellipsis/(UO/sub 2/Cl/sub 4/)/sup 2/minus// interaction. The dibenzo-18-crown-6 complexed ammonium ions are 1:1 and form bifurcated hydrogen bonds with the chlorine atoms in the (UO/sub 2/Cl/sub 4/)/sup /minus// anion. The formation of (Na(12-crown-4)/sub 2//sub 2/(UO/sub 2/Cl/sub 4/) /times/ 2OHMe and (UO/sub 2/Cl/sub 2/(OH)/sub 2/)/sub 3/) /times/ 18-crown-6 /times/ H/sub 2/O /times/ OHMe has been confirmed by preliminary single-crystal X-ray diffraction studies.« less
  • 6-H perovskites with compositions Ba{sub 2}Co{sub 2-x}Sb{sub x}O{sub 6-y}, 0.6{<=}x{<=}0.8 and x=1.33 (Ba{sub 3}CoSb{sub 2}O{sub 9}) have been prepared in air at 1150 deg. C. Refinements of the crystal structures of Ba{sub 2}Co{sub 1.4}Sb{sub 0.6}O{sub 6-y} and Ba{sub 3}CoSb{sub 2}O{sub 9} were performed in space group P6{sub 3}/mmc, using neutron and X-ray powder diffraction data, respectively: Ba{sub 2}Co{sub 1.4}Sb{sub 0.6}O{sub 6-y} a=5.7315(1) A, c=14.1118(4) A, R{sub F}{sup 2}=0.0669, R{sub p}=0.0464, {chi}{sup 2}=1.39; Ba{sub 3}CoSb{sub 2}O{sub 9} a=5.85321(7) A, c=14.4454(2) A, R{sub F}{sup 2}=0.0458, R{sub p}=0.0258, {chi}{sup 2}=1.24. In Ba{sub 3}CoSb{sub 2}O{sub 9} the antimony atoms are located in pairs ofmore » face-sharing octahedra separated by cobalt atoms in octahedral layers, while in Ba{sub 2}Co{sub 1.4}Sb{sub 0.6}O{sub 6-y} a random distribution of B cations was found. In the latter structure, oxygen vacancies are preferably located in BaO{sub 3} planes separating the face-sharing octahedra. Electron diffraction and high-resolution electron microscopy studies showed that the structures are well ordered. Results of the magnetic susceptibility measurements of Ba{sub 3}CoSb{sub 2}O{sub 9} and Ba{sub 2}Co{sub 1.4}Sb{sub 0.6}O{sub 6-y} are reported.« less
  • A new family of mixed oxides of general formula Ti{sub 3(1{minus}x)}Ni{sub x}Sb{sub 2x}O{sub 6} for 1.0 {ge} x {ge} 0.6 has been synthesized, by solid state reaction in air, and the crystallographic data for these oxides have been determined. The structures of these compounds are related to the rutile or trirutile type structure. Magnetic susceptibility measurements, between 4.2 and 300 K, show the existence of a broad maximum centered at about 35 K for the NiSb{sub 2}O{sub 6} oxide which has been fitted by using the high temperature series expansion method (HTSE) and the estimated value of the exchange integralmore » is {minus}7 K. This bidimensional antiferromagnetic ordering is drastically lowered when the x value increases for the different doped phases in the system Ti{sub 3(1{minus}x)}Ni{sub x}Sb{sub 2x}O{sub 6}.« less