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1.
Ternary lanthanide rhenium oxides Ln3ReO7 (Ln=Sm, Eu, Ho) were prepared and their structures were determined by X-ray diffraction measurements. They crystallize in an orthorhombic superstructure of cubic fluorite (space group Cmcm for Ln=Sm, Eu; C2221 for Ln=Ho). The magnetic properties were characterized by magnetic susceptibility and specific heat measurements from 1.8 to 400 K. The Sm3ReO7 shows an antiferromagnetic transition at 1.9 K. The Eu3ReO7 indicates a magnetic anomaly at 12 K. On the other hand, the results of the specific heat measurements indicate that both Sm3ReO7 and Eu3ReO7 undergo a structure transition at 270 and 350 K, respectively. The Ho3ReO7 is paramagnetic down to 1.8 K.  相似文献   

2.
A series of rare-earth iron borates having general formula LnFe3(BO3)4 (Ln=Y, La-Nd, Sm-Ho) were prepared and their magnetic properties have been investigated by the magnetic susceptibility, specific heat, and 57Fe Mössbauer spectrum measurements. These borates show antiferromagnetic transitions at low temperatures and their magnetic transition temperatures increase with decreasing Ln3+ ionic radius from 22 K for LaFe3(BO3)4 to 40 K for TbFe3(BO3)4. In addition, X-ray diffraction, specific heat, and differential thermal analysis (DTA) measurements indicate that the phase transition occurs for the LnFe3(BO3)4 compounds with Ln=Eu-Ho, Y, and its transition temperature increases remarkably with decreasing Ln3+ ionic radius from 88 K for Ln=Eu to 445 K for Ln=Y.  相似文献   

3.
The crystal structures and magnetic properties of the quaternary lanthanide oxides Ba6Ln2Fe4O15 (Ln=Pr and Nd) are reported. They crystallize in a hexagonal structure with space group P63mc and have the “Fe4O15 cluster” consisting of one FeO6 octahedron and three FeO4 tetrahedra. Measurements of the magnetic susceptibility, specific heat, and powder neutron diffraction reveal that this cluster behaves as a spin tetramer with a ferrimagnetic ground state of ST=5 even at room temperature. The cluster moments show a long-range antiferromagnetic ordering at 23.2 K (Ln=Pr) and 17.8 K (Nd), and the magnetic moments of the Ln3+ ions also order cooperatively. By applying the magnetic field (∼2 T), this antiferromagnetic ordering of the clusters changes to a ferromagnetic one. This result indicates that there exists a competition in the magnetic interaction between the clusters.  相似文献   

4.
Magnetic properties and structural transitions of ternary rare-earth transition-metal oxides Ln3MO7 (Ln=rare earths, M=transition metals) were investigated. In this study, we prepared a series of molybdates Ln3MoO7 (Ln=La-Gd). They crystallize in an orthorhombic superstructure of cubic fluorite with space group P212121, in which Ln3+ ions occupy two different crystallographic sites (the 8-coordinated and 7-coordinated sites). All of these compounds show a phase transition from the space group P212121 to Pnma in the temperature range between 370 and 710 K. Their magnetic properties were characterized by magnetic susceptibility measurements from 1.8 to 400 K and specific heat measurements from 0.4 to 400 K. Gd3MoO7 shows an antiferromagnetic transition at 1.9 K. Measurements of the specific heat for Sm3MoO7 and the analysis of the magnetic specific heat indicate a “two-step” antiferromagnetic transition due to the ordering of Sm magnetic moments in different crystallographic sites, i.e., with decreasing temperature, the antiferromagnetic ordering of the 7-coordinated Sm ions occur at 2.5 K, and then the 8-coordinated Sm ions order at 0.8 K. The results of Ln3MoO7 were compared with the magnetic properties and structural transitions of Ln3MO7 (M=Nb, Ru, Sb, Ta, Re, Os, or Ir).  相似文献   

5.
Ternary rare earth antimonates Ln3SbO7 (Ln=rare earths) were prepared and their structures were determined by X-ray diffraction measurements. They crystallize in an orthorhombic superstructure of cubic fluorite (space group Cmcm for Ln=La, Pr, Nd; C2221 for Ln=Nd-Lu), in which Ln3+ ions occupy two different crystallographic sites (the 8-coordinated and 7-coordinated sites). Their magnetic properties were characterized by magnetic susceptibility and specific heat measurements from 1.8 to 400 K. The Ln3SbO7 (Ln=Nd, Gd-Ho) compounds show an antiferromagnetic transition at 2.2-3.2 K. Sm3SbO7 and Eu3SbO7 show van Vleck paramagnetism. Measurements of the specific heat down to 0.4 K for Gd3SbO7 and the analysis of the magnetic specific heat indicate that the antiferromagnetic ordering of the 8-coordinated Gd ions occur at 2.6 K, and the 7-coordinated Gd ions order at a furthermore low temperature.  相似文献   

6.
Ternary lanthanide-molybdenum oxides Ln3MoO7 (Ln=La, Pr, Nd, Sm, Eu) have been prepared. Their structures were determined by X-ray diffraction measurements. They crystallize in a superstructure of cubic fluorite and the space group is P212121. The Mo ion is octahedrally coordinated by six oxygens and the slightly distorted octahedra share corners forming a zig-zag chain parallel to the b-axis. These compounds have been characterized by magnetic susceptibility and specific heat measurements. The La3MoO7 shows complex magnetic behavior at 150 and 380 K. Below these temperatures, there is a large difference in the temperature-dependence of the magnetic susceptibility measured under zero-field-cooled condition and under field-cooled condition. The Nd3MoO7 show a clear antiferromagnetic transition at 2.5 K. From the susceptibility measurements, both Pr3MoO7 and Sm3MoO7 show the existence of magnetic anomaly at 8.0 and 2.5 K, respectively. The results of the specific heat measurements also show anomalies at the corresponding magnetic transition temperatures. The differential scanning calorimetry measurements indicate that two phase-transitions occur for any Ln3MoO7 compound in the temperature range between 370 and 710 K.  相似文献   

7.
Quadruple perovskites Ba4LnRu3O12 (Ln=La, Nd, Sm-Gd, Dy-Lu) were prepared and their magnetic properties were investigated. They adopt the 12L-perovskite-type structure consisting of Ru3O12 trimers and LnO6 octahedra. All of these compounds show an antiferromagnetic transition at 2.5-30 K. For Ba4NdRu3O12, ferrimagnetic ordering has been observed at 11.5 K. The observed magnetic transition is due to the magnetic behavior of the Ru4.33+3O12 trimer with S=. Magnetic properties of Ba4LnRu3O12 were compared with those of triple perovskites Ba3LnRu2O9 and double perovskites Ba2LnRuO6.  相似文献   

8.
Single crystals of Ln5Ru2O12 (Ln=Pr, Nd, Sm-Tb) were grown out of either NaOH or KOH fluxes in sealed silver tubes. The crystals of all the phases were observed to be twinned as confirmed by TEM studies. The series crystallize in the C2/m monoclinic system with lattice parameters, a=12.4049(4)-12.7621(6) Å, b=5.8414(2)-5.9488(3) Å, c=7.3489(2)-7.6424(4) Å, β=107.425(3)-107.432(2)° and Z=2. The crystal structure is isotypic with the defect/disorder model of Ln5Re2O12 (Ln = Y, Gd) and consists of one dimensional edge shared RuO6 octahedral chains separated by a two dimensional LnOx polyhedral framework. Magnetic measurements indicate paramagnetic and antiferromagnetic behavior for Ln=Nd, Sm-Gd and Ln=Tb, respectively.  相似文献   

9.
Layered lanthanide hydroxynitrate anion exchange host lattices have been prepared via a room temperature precipitation synthesis. These materials have the composition Ln2(OH)5NO3·H2O and are formed for Y and the lanthanides from Eu to Er and as such include the first Eu containing nitrate anion exchange host lattice. The interlayer separation of these materials, approximately 8.5 Å, is lower than in the related phases Ln2(OH)5NO3·1.5H2O which have a corresponding value of 9.1 Å and is consistent with the reduction in the co-intercalated water content of these materials. These new intercalation hosts have been shown to undergo facile anion exchange reactions with a wide range of organic carboxylate and sulfonate anions. These reactions produce phases with up to three times the interlayer separation of the host lattice demonstrating the flexibility of these materials.  相似文献   

10.
Ternary iridium oxides Ln3IrO7 (Ln=Pr, Nd, Sm, and Eu) were prepared and their crystal structures, magnetic and thermal properties were investigated. Powder X-ray diffractions (XRDs) were measured for all samples and neutron diffraction (ND) measurements were performed for Pr3IrO7. All the profiles were refined with space group Cmcm (No. 63). The lattice parameters for Pr3IrO7 refined by using ND data are a=10.9782(13) Å, b=7.4389(9) Å, and c=7.5361(9) Å. From specific heat and differential thermal analysis (DTA) measurements, Ln3IrO7 (Ln=Pr, Nd, Sm, and Eu) show thermal anomalies at 261, 342, 420, and 485 K, respectively. The results of powder high-temperature XRD and ND measurements indicate that these anomalies are due to the structural phase transition. Magnetic susceptibilities of these compounds were measured in the temperature range between 1.8 and 400 K. Nd3IrO7 shows an antiferromagnetic transition at 2.6 K. A specific heat anomaly has also been observed at the same temperature. For Ln3IrO7 (Ln=Pr, Sm, and Eu), no magnetic anomalies have been found in the experimental temperature range.  相似文献   

11.
The potassium lanthanide double sulphates KLn(SO4)2·H2O (Ln=La, Nd, Sm, Eu, Gd, Dy) were obtained by evaporation of aqueous reaction mixtures of rare earth (III) sulphates and potassium thiocyanate at 298 K. X-ray single-crystal investigations show that KLn(SO4)2·H2O (Ln=Nd, Sm, Eu, Gd, Dy) crystallise monoclinically (Ln=Sm: P21/c, Z=4, a=10.047(1), b=8.4555(1), c=10.349(1) Å, wR2=0.060, R1=0.024, 945 reflections, 125 parameters) while KLa(SO4)2·H2O adopts space group P3221 (Z=3, a=7.1490(5), c=13.2439(12) Å, wR2=0.038, R1=0.017, 695 reflections, 65 parameters). The coordination environment of the lanthanide ions in KLn(SO4)2·H2O is different in the case of the Nd/Sm/Gd and the Eu/Dy compounds, respectively. In the first case the Ln atoms are nine-fold coordinated in contrast to the latter where the Ln ions are eight-fold coordinated by oxygen atoms. The vibrational spectra of KLn(SO4)2·H2O and the UV-vis reflection spectra of KEu(SO4)2·H2O and KNd(SO4)2·H2O are also reported.  相似文献   

12.
Seven new quaternary metal sulfides, KY2CuS4, KNd2CuS4, KSm2CuS4, KTb2CuS4, KHo2CuS4, K2Dy4Cu4S9, and K2Ho4Cu4S9, were prepared by the reactive flux method. All crystallographic data were collected at 153 K. The isostructural compounds KLn2CuS4 (Ln=Y, Nd, Sm, Tb, Ho) crystallize in space group Cmcm of the orthorhombic system with four formula units in cells of dimensions (Ln, a, b, c (Å)): Y, 3.9475(9), 13.345(3), 13.668(3); Nd, 4.0577(3), 13.7442(10), 13.9265(10); Sm, 4.0218(4), 13.6074(14), 13.8264(14); Tb, 3.9679(5), 13.4243(17), 13.7102(18); Ho, 3.9378(3), 13.3330(11), 13.6487(11). The corresponding R1 indices for the refined structures are 0.0197, 0.0153, 0.0158, 0.0181, and 0.0178. The isostructural compounds K2Dy4Cu4S9 and K2Ho4Cu4S9 crystallize in space group C2/m of the monoclinic system with two formula units in cells of dimensions (Ln, a, b, c (Å), β (°)): Dy, 13.7061(13), 3.9482(4), 15.8111(15), 109.723(1); Ho, 13.6760(14), 3.9360(4), 15.7950 (16), 109.666(2). The corresponding R1 indices are 0.0312 and 0.0207. Both structure types are closely related three-dimensional tunnel structures. The tunnels are filled with bicapped trigonal-prismatically coordinated K atoms. Their anionic frameworks are built from LnS6 octahedra and CuS4 tetrahedra. KLn2CuS4 contains 1[CuS35−] chains of vertex-sharing tetrahedra and K2Ln4Cu4S9 contains 1[Cu4S812−] chains of tetrahedra. K2Ho4Cu4S9 shows Curie-Weiss paramagnetic behavior between 5 and 300 K, and has an effective magnetic moment of 10.71 μB for Ho3+ at 293 K. Optical band gaps of 2.17 eV for KSm2CuS4 and 2.43 eV for K2Ho4Cu4S9 were deduced from diffuse reflectance spectra. A first-principles calculation of the density of states and the frequency-dependent optical conductivity was performed on KSm2CuS4. The calculated band gap of 2.1 eV is in good agreement with the experimental value.  相似文献   

13.
Two types of lanthanide selenidoantimonates [Ln(en)4(SbSe4)] (Ln=Ce(1a), Pr(1b)) and [Ln(en)4]SbSe4·0.5en (Ln=Eu(2a), Gd(2b), Er(2c), Tm(2d), Yb(2e); en=ethylenediamine) were solvothermally synthesized by reactions of LnCl3, Sb and Se with the stoichiometric ratio in en solvent at 140 °C. The four-en coordinated lanthanide complex cation [Ln(en)4]3+ formed in situ balances the charge of SbSe43− anion. In compounds 1a and 1b, the SbSe43− anion act as a monodentate ligand to coordinate complex [Ln(en)4]3+ and the neutral compound [Ln(en)4(SbSe4)] is formed. The Ln3+ ion has a nine-coordinated environment involving eight N atoms and one Se atom forming a distorted monocapped square antiprism. In 2a-2e the lanthanide(III) ion exists as isolated complex [Ln(en)4]3+, in which the Ln3+ ion is in a bicapped trigonal prism geometry. A systematic investigation of the crystal structures reveals that two types of structural features of these lanthanide selenidoantimonates are related with lanthanides contraction across the lanthanide series. TG curves show that compounds 1a-1b and 2a-2e remove their organic components in one and two steps, respectively.  相似文献   

14.
Crystal structures and magnetic properties of the ternary oxides Ln3NbO7 (Ln=La, Pr, Nd, Sm-Lu) are reported. Their powder X-ray diffraction measurements and Rietveld analyzes show that they have the fluorite-related structures with space group Pnma (Ln=La, Pr, Nd), C2221 (Ln=Sm-Tb), or Fm-3m (Ln=Dy-Lu). Magnetic susceptibility measurements were carried out from 1.8 to 400 K. The Ln3NbO7 compounds for Ln=Pr, Gd, Dy-Yb show Curie-Weiss paramagnetic behavior, and Sm3NbO7 and Eu3NbO7 show van Vleck paramagnetism. On the other hand, two magnetic anomalies were observed for both Nd3NbO7 (0.6 and 2.7 K) and Tb3NbO7 (2.0 and 3.2 K). From the results of specific heat measurements, it was found that these anomalies are due to the antiferromagnetic ordering of Ln ions in two different crystallographic sites (the 8-coordinated and 7-coordinated sites).  相似文献   

15.
Ln3Co4Sn13 (Ln=La, Ce) have been synthesized by flux growth and characterized by single crystal X-ray diffraction. These compounds adopt the Yb3Rh4Sn13-type structure and crystallize in the cubic space group (No. 223) with Z=2. Lattice parameters at 298 K are , , and , for the La and Ce analogues, respectively. The crystal structure consists of an Sn-centered icosahedron at the origin of the unit cell, which shares faces with eight Co trigonal prisms and 12 Ln-centered cuboctahedra. Magnetization data at 0.1 T show paramagnetic behavior down to 1.8 K for Ce3Co4Sn13, with per Ce3+, while conventional type II superconductivity appears below 2.85 K in the La compound. Electrical resistivity and specific heat data for the La compound show a corresponding sharp superconducting transition at Tc∼2.85 K. The entropy and resistivity data for Ce3Co4Sn13 show the existence of the Kondo effect with a complicated semiconducting-like behavior in the resistivity data. In addition, a large enhanced specific heat coefficient at low T with a low magnetic transition temperature suggests a heavy-fermionic character for the Ce compound. Herein, the structure and physical properties of Ln3Co4Sn13 (Ln=La, Ce) are discussed.  相似文献   

16.
We describe the preparation, structure determination and magnetic properties of two Ba perovskites containing rare-earth cations at the B-sublattice. Ba3Ln2MoO9 (Ln=Ho3+ and Er3+) were synthesized by ceramic procedures. Joint X-ray (XRPD) and neutron (NPD) powder diffraction refinements were carried out to analyse the crystal structure. At room temperature, both phases are tetragonal, space group I4/mcm, Z=4. Ln and Mo atoms are found to be distributed at random over the octahedral sites of the perovskites. Magnetic measurements at 0.1 T show that both samples are paramagnetic between 3 and 300 K, following a Curie-Weiss law. M vs. H curves show a region of paramagnetic behaviour and above 2.5 T a magnetic saturated system is observed. Finally, the temperature evolution of the NPD patterns of Ba3Ho2MoO9 reveals the absence of long-range magnetic ordering down to 2 K.  相似文献   

17.
Structures and magnetic properties of double perovskite-type oxides Eu2LnTaO6 (Ln=Eu, Dy-Lu) were investigated. These compounds adopt a distorted double perovskite structure with space group P21/n. Magnetic susceptibility, specific heat, and 151Eu Mössbauer spectrum measurements show that the Eu2+ ions at the 12-coordinate sites of the perovskite structure are antiferromagnetically ordered at ∼4 K, and that Ln3+ ions at the 6-coordinate site are in the paramagnetic state down to 1.8 K.  相似文献   

18.
Colorless single crystals of Gd(IO3)3 or pale pink single crystals of Er(IO3)3 have been formed from the reaction of Gd metal with H5IO6 or Er metal with H5IO6 under hydrothermal reaction conditions at 180 °C. The structures of both materials adopt the Bi(IO3)3 structure type. Crystallographic data are (MoKα, λ=0.71073 Å): Gd(IO3)3, monoclinic, space group P21/n, a=8.7615(3) Å, b=5.9081(2) Å, c=15.1232(6) Å, β=96.980(1)°, V=777.03(5) Z=4, R(F)=1.68% for 119 parameters with 1930 reflections with I>2σ(I); Er(IO3)3, monoclinic, space group P21/n, a=8.6885(7) Å, b=5.9538(5) Å, c=14.9664(12) Å, β=97.054(1)°, V=768.4(1) Z=4, R(F)=2.26% for 119 parameters with 1894 reflections with I>2σ(I). In addition to structural studies, Gd(IO3)3, Er(IO3)3, and the isostructural Yb(IO3)3 were also characterized by Raman spectroscopy and magnetic property measurements. The results of the Raman studies indicated that the vibrational profiles are adequately sensitive to distinguish between the structures of the iodates reported here and other lanthanide iodate systems. The magnetic measurements indicate that only in Gd(IO3)3 did the 3+ lanthanide ion exhibit its full 7.9 μB Hund's rule moment; Er3+ and Yb3+ exhibited ground state moments and gap energy scales of 8.3 μB/70 K and 3.8 μB/160 K, respectively. Er(IO3)3 exhibited extremely weak ferromagnetic correlations (+0.4 K), while the magnetic ions in Gd(IO3)3 and Yb(IO3)3 were fully non-interacting within the resolution of our measurements (∼0.2 K).  相似文献   

19.
The quaternary oxychalcogenides Ln4MnOSe6 (Ln=La, Ce, Nd), Ln4FeOSe6 (Ln=La, Ce, Sm), and La4MnOS6 have been synthesized by the reactions of Ln (Ln=La, Ce, Nd, Sm), M (M=Mn, Fe), Se, and SeO2 at 1173 K for the selenides or by the reaction of La2S3 and MnO at 1173 K for the sulfide. Warning: These reactions frequently end in explosions. These isostructural compounds crystallize with two formula units in space group of the hexagonal system. The cell constants (a, c in Å) at 153 K are: La4MnOSe6, 9.7596(3), 7.0722(4); La4FeOSe6, 9.7388(4), 7.0512(5); Ce4MnOSe6, 9.6795(4), 7.0235(5); Ce4FeOSe6, 9.6405(6), 6.9888(4); Nd4MnOSe6, 9.5553(5), 6.9516(5); Sm4FeOSe6, 9.4489(5), 6.8784(5); and La4MnOS6, 9.4766(6), 6.8246(6). The structure of these Ln4MOQ6 compounds comprises a three-dimensional framework of interconnected LnOQ7 bicapped trigonal prisms, MQ6 octahedra, and the unusual LnOQ6 tricapped tetrahedra.  相似文献   

20.
Single crystals of double-perovskite type lanthanide magnesium iridium oxides, Ln2MgIrO6 (Ln=Pr, Nd, Sm-Gd) have been grown in a molten potassium hydroxide flux. The compounds crystallize in a distorted 1:1 rock salt lattice, space group P21/n, consisting of corner shared MO6 (M=Mg2+ and Ir4+) octahedra, where the rare earth cations occupy the eight-fold coordination sites formed by the corner shared octahedra. Pr2MgIrO6, Nd2MgIrO6, Sm2MgIrO6, and Eu2MgIrO6 order antiferromagnetically around 10-15 K.  相似文献   

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