The extended chain compounds Ln12(C2)3I17 (Ln=Pr, Nd, Gd, Dy): Synthesis, structure and physical properties

The title compounds are obtained in high yield from stoichiometric mixtures of Ln, LnI₃ and graphite, heated at 900-950 °C in welded Ta containers. The crystal structures of new Pr and Nd phases determined by single-crystal X-ray diffraction are related to those of other Ln₁₂(C₂)₃I₁₇-type compounds (C 2/c, a=19.610(1) and 19.574(4) Å, b=12.406(2) and 12.393(3) Å, c=19.062(5) and 19.003(5) Å, β=90.45(3)° and 90.41(3)°, for Pr₁₂(C₂)₃I₁₇ and Nd₁₂(C₂)₃I₁₇, respectively). All compounds contain infinite zigzag chains of C₂-centered metal atom octahedra condensed by edge-sharing into the [tcc]_∞ sequence (c=cis, t=trans) and surrounded by edge-bridging iodine atoms as well as by apical iodine atoms that bridge between chains. The polycrystalline Gd₁₂(C₂)₃I₁₇ sample exhibits semiconducting thermal behavior which is consistent with an ionic formulation (Ln³⁺)₁₂(C₂^6-)₃(I⁻)₁₇(e⁻) under the assumption that one extra electron is localized in metal-metal bonding. The magnetization measurements on Nd₁₂(C₂)₃I₁₇, Gd₁₂(C₂)₃I₁₇ and Dy₁₂(C₂)₃I₁₇ indicate the coexistence of competing magnetic interactions leading to spin freezing at T_f=5 K for the Gd phase. The Nd and Dy compounds order antiferromagnetically at T_N=25 and 29 K, respectively. For Dy₁₂(C₂)₃I₁₇, a metamagnetic transition is observed at a critical magnetic field H≈25 kOe.     

Photoluminescence of Ce, Pr and Tb activated Sr3Ln(PO4)3 under VUV-UV excitation

The spectroscopic properties in VUV-Vis range for the eulytite structural phosphors Sr₃Gd(PO₄)₃:Ln³⁺ (Ln³⁺=Ce³⁺, Pr³⁺, Tb³⁺), Sr₃Ce(PO₄)₃, Sr₃Gd(PO₄)₃ and Sr₃Tb(PO₄)₃ were investigated. The bands near 170 nm in VUV excitation spectra are assumed to connect with the host lattices related absorption. The f-d transitions of Ce³⁺, Pr³⁺ and Tb³⁺ in the host lattices are assigned and corroborated. A convenient experiment formulation on the relationship between the lowest f-d transition energies and n value for trivalent 4fⁿ-series rare earth ions in these host lattices is applied.     

Synthesis, structure, and magnetism of Tb4PdGa12 and Tb4PtGa12

Single crystals of Tb₄MGa₁₂ (M=Pd, Pt) have been synthesized. The isostructural compounds crystallize in the cubic space group , with Z=2 and lattice parameters: a=8.5940(5) and 8.5850(3) Å for Tb₄PdGa₁₂ and Tb₄PtGa₁₂, respectively. The crystal structure consists of corner-sharing MGa₆ octahedra and TbGa₃ cuboctahedra. Magnetic measurements suggest that Tb₄PdGa₁₂ is an antiferromagnetic metamagnet with a Néel temperature of 16 K, while the Pt analog orders at T_N=12 K.     

Magnetic properties of Fe2P-type Tb6FeTe2, Tb6CoTe2, Tb6NiTe2 and Er6FeTe2 compounds

The magnetic ordering of the Fe₂P-type Tb₆FeTe₂, Tb₆CoTe₂ Tb₆NiTe₂ and Er₆FeTe₂ phases (space group P6¯2m) has been investigated through magnetization measurement and neutron powder diffraction. Tb₆FeTe₂, Tb₆CoTe₂ and Tb₆NiTe₂ demonstrate high-temperature ferromagnetic and low-temperature spin reorientation transitions, whereas Er₆FeTe₂ shows antiferromagnetic transition, only.The Tb₆FeTe₂ and Tb₆NiTe₂ phases show same high-temperature collinear ferromagnetic structure, whereas Tb₆FeTe₂ is the commensurate non-collinear ferromagnet and Tb₆NiTe₂ is the canted ferromagnetic cone with K₁=[0, 0, ±3/10] and K₂=[±2/9, ±2/9, 0] wave vectors at 2 K. The magnetic structure of Er₆FeTe₂ is a flat spiral with K₁=[0, 0, ±1/10] at 2 K. The magnetic entropy change for Tb₆NiTe₂ is ΔS_m=−4.86 J/kg K at 229 K for the field change Δμ₀H=0-5 T.In addition, novel Fe₂P-type Gd₆FeTe₂, Zr₆FeTe₂, Hf₆FeTe₂, Dy₆NiTe₂, Zr₆NiTe₂ and Hf₆NiTe₂ phases have been obtained.     

Structure, stoichiometry and magnetic properties of the low-dimensional structure phase LiCuVO4

A systematic investigation of a series of single- and polycrystalline LiCuVO₄ samples by means of X-ray diffraction, X-ray photoelectron spectroscopy, differential dissolution analysis, and magnetic susceptibility measurement were performed. This study reveals a noticeable difference in stoichiometry and structure of the samples prepared in different ways. The magnetic properties are discussed with respect to phase inhomogeneity, non-stoichiometry and structural defects.     

Synthesis,structure and magnetism of a novel Cu4^ⅡTi5^Ⅳ heterometallic cluster

A nonanuclear Cu4^ⅡTi5^Ⅳheterometallic cluster,[Ti5 Cu4 O6(ba)(16)](1,Hba=benzoic acid)was synthesized in one-pot reaction under the solvothermal condition.The metallic skeleton 1 contains a Ti5 core constructed from two vertex-shared Ti3 triangles and four separated Cu atoms outside which are connected together byμ3-O^2- ions.Total 16 ba ligands adoptμ2-η^1:η^1 coordination mode to protect the overall hetero metallic co re.Due to the unique d-d transitions of Cu^Ⅱion,the reflectance spectrum of 1 displays broad and strong absorption towards visible light extending to the near-infrared region.Moreover,1 shows almost purely paramagnetic behavior with the presence of weak antiferromagnetic interactions at low temperatures.     

Synthesis and magnetic properties of ALnO2 (A=Cu or Ag; Ln=rare earths) with the delafossite structure

Synthesis, structures, and magnetic properties of ternary rare earth oxides ALnO₂ (A=Cu or Ag; Ln=rare earths) have been investigated. CuLnO₂ (Ln=La, Pr, Nd, Sm, Eu) were synthesized by the direct solid state reaction of Cu₂O and Ln₂O₃, and AgLnO₂ (Ln=Tm, Yb, Lu) were obtained by the cation-exchange reaction of NaLnO₂ and AgNO₃ in a KNO₃ flux. These compounds crystallized in the delafossite-type structure with the rhombohedral 3R type (space group: R-3m). Magnetic susceptibility measurements showed that these compounds are paramagnetic down to 1.8 K. Specific heat measurements down to 0.4 K indicated that CuNdO₂ ordered antiferromagnetically at 0.8 K.     

Lattice distortions in layered type arsenides LnTAs2 (Ln=La-Nd, Sm, Gd, Tb; T=Ag, Au): Crystal structures, electronic and magnetic properties

The lanthanide coinage-metal diarsenides LnTAs₂ (Ln=La, Ce-Nd, Sm; T=Ag, Au) have been reinvestigated and their structures have been refined from single crystal X-ray data. Two different distortion variants of the HfCuSi₂ type are found: PrAgAs₂, NdAgAs₂, SmAgAs₂, GdAgAs₂, TbAgAs₂, NdAuAs₂ and SmAuAs₂ crystallize as twofold superstructures in space group Pmcn with the As atoms of their planar layers forming zigzag chains, whereas LaAgAs₂, CeAgAs₂ and PrAuAs₂ adopt a fourfold superstructure (space group Pmca) with cis-trans chains of As atoms. The respective atomic positions can be derived from the HfCuSi₂ type by group-subgroup relations. The compounds with zigzag chains of As atoms exhibit metallic behaviour while those with cis-trans chains are semiconducting as measured on powder pellets. The majority of the compounds including 4f elements show antiferromagnetic ordering at T_N<20 K.     

Photoluminescence and energy transfer in Tb/Mn co-doped ZnAl2O4 glass ceramics

We report on Tb³⁺ as efficient sensitizer for red photoemission from Mn²⁺-centers in ZnO-B₂O₃-Al₂O₃-Si₂O-Na₂O-SrO glasses and corresponding gahnite glass ceramics. In comparison to singly or co-doped glasses, the glass ceramics exhibit significantly increased emission intensity. Structural considerations, ESR, and dynamic luminescence spectroscopy indicate partial incorporation of Mn²⁺ as well as Tb³⁺ into the crystalline phase, the former on octahedral Zn²⁺-sites. Interionic distance and charge transfer probability between both species depend on crystallization conditions. This enables control of the energy transfer process and, hence, tunability of the color of photoemission by simultaneous emission from Tb³⁺ and Mn²⁺ centers. Concentration quenching in Mn²⁺-singly doped materials was found at a critical dopant concentration of about 1.0 mol%. The energy transfer process was studied in detail by dynamic as well as static luminescence spectroscopy. Spectroscopic results suggest the application of the studied materials as single or dual-mode emitting phosphor for luminescent lighting.     

Structure and magnetic properties of rare-earth chromium germanides RECrxGe2 (RE=Sm, Gd-Er)

The ternary rare-earth chromium germanides RECr_xGe₂ (RE=Sm, Gd-Er) have been obtained by reactions of the elements, either in the presence of tin or indium flux, or through arc-melting followed by annealing at 800 °C. The homogeneity range is limited to 0.25?x?0.50 for DyCr_xGe₂. Single-crystal and powder X-ray diffraction studies on the RECr_0.3Ge₂ members revealed that they adopt the CeNiSi₂-type structure (space group Cmcm, Z=4, a=4.1939(5)-4.016(2) Å, b=16.291(2)-15.6579(6) Å, c=4.0598(5)-3.9876(2) Å in the progression for RE=Sm to Er), which can be considered to be built up by stuffing transition-metal atoms into the square pyramidal sites of a “REGe₂” host with the ZrSi₂-type structure. (The existence of YbCr_0.3Ge₂ is also implicated.) Only the average structure was determined here, because unusually short Cr-Ge distances imply the development of a superstructure involving distortions of the square Ge net. Magnetic measurements on RECr_0.3Ge₂ (RE=Gd-Er) indicated that antiferromagnetic ordering sets in below T_N (ranging from 3 to 17 K), with additional transitions observed at lower temperatures for the Tb and Dy members.     

Syntheses, crystal structures and spectroscopic properties of KEu[AsS4], K3Dy[AsS4]2 and Rb4Nd0.67[AsS4]2

Three rare earth compounds, KEu[AsS₄] (1), K₃Dy[AsS₄]₂ (2), and Rb₄Nd_0.67[AsS₄]₂ (3) have been synthesized employing the molten flux method. The reactions of A₂S₃ (A = K, Rb), Ln (Ln = Eu, Dy, Nd), As₂S₃, S were accomplished at 600 °C for 96 h in evacuated fused silica ampoules. Crystal data for these compounds are: 1, monoclinic, space group P2₁/m (no. 11), a = 6.7276(7) Å, b = 6.7190(5) Å, c = 8.6947(9) Å, β = 107.287(12)°, Z = 2; 2, monoclinic, space group C2/c (no. 15), a = 10.3381(7) Å, b = 18.7439(12) Å, c = 8.8185(6) Å, β = 117.060(7)°, Z = 4; 3, orthorhombic, space group Ibam (no. 72), a = 18.7333(15) Å, b = 9.1461(5) Å, c = 10.2060(6) Å, Z = 4. 1 is a two-dimensional structure with ²_∞[Eu(AsS₄)]⁻ layers separated by potassium cations. Within each layer, distorted bicapped trigonal [EuS₈] prisms are linked through distorted [AsS₄]³⁻ tetrahedra. Each Eu²⁺ cation is coordinated by two [AsS₄]³⁻ units by edge-sharing and bonded to further two [AsS₄]³⁻ units by corner-sharing. Compound 2 contains a one-dimensional structure with ¹_∞[Dy(AsS₄)₂]³⁻ chains separated by potassium cations. Within each chain, distorted bicapped trigonal prisms of [DyS₈] are linked by slightly distorted [AsS₄]³⁻ tetrahedra. Each Dy³⁺ ion is surrounded by four [AsS₄]³⁻ moieties in an edge-sharing fashion. For compound 3 also a one-dimensional structure with ¹_∞[Nd₀.₆₇(AsS₄)₂]⁴⁻ chains is observed. But the Nd position is only partially occupied and overall every third Nd atom is missing along the chain. This cuts the infinite chains into short dimers containing two bridging [As₄]³⁻ units and four terminal [AsS₄]³⁻ groups. 1 is characterized with UV/vis diffuse reflectance spectroscopy, IR, and Raman spectra.     

Synthesis, crystal structure and magnetic properties of the spin ladder compounds La2(Cu1−xZnx)2O5 and La8(Cu1−xZnx)7O19

The influence of Zn-doping on the crystal structure and magnetic properties of the spin ladder compounds La₂Cu₂O₅ (4-leg) and La₈Cu₇O₁₉ (5-leg) have been investigated. The La₂(Cu_1−xZn_x)₂O₅ and La₈(Cu_1−xZn_x)₇O₁₉ solid solutions were obtained as single phases with x=0-0.1 via the solid-state reaction method in the temperature range between 1005-1010 °C and 1015-1030 °C in oxygen and air atmospheres, respectively. The lattice parameters a and c of the monoclinic crystal structures as well as the unit cell volume V increase with increasing x, while b and β decrease for both series. The magnetic susceptibilities χ of both series show a very similar behavior on temperature as well as on Zn-doping, which is supposed to be due to the similar Cu-O coordination in both La₂Cu₂O₅ and La₈Cu₇O₁₉. For low Zn-doping (x?0.04), a spin-chain like behavior is found. This quasi-one-dimensional behavior is strongly suppressed in both series for x?0.04. Here, the maximum (characteristic for spin chains) in χ(T) disappears and χ(T) decreases monotonically with increasing temperature.     

Synthesis,structure and magnetic properties of a decanuclear Fe(III)/oxo cluster

An iron (III) cluster, namely [Fe₁₀(μ₃–O)₈L₈(NO₃)₆] (1), has been synthesized by treatment of Fe(NO₃)₃·9H₂O with 3,5–dimethyl–1–(hydroxymethyl)–pyrazole (HL) under ambient temperature. The core skeleton of {Fe^III₁₀} can be regarded as a pear-like cage with eight triangular {Fe^III₃(μ₃–O)} units, in which each three Fe^III centers is held together by one μ₃–O²⁻ group with Fe^III centers as corner-sharing triangle units. Importantly, {Fe^III₁₀} cluster is not only stable in solid state but also in solution, which is confirmed by powder X-ray diffraction (PXRD) pattern and electrospray ionization mass spectrometry (ESI-MS), respectively. Furthermore, 1 shows antiferromagnetic exchange behavior arising from the interactions between the iron(III) centers.     

Spin-glass behavior in Pr0.7Ca0.3CoO3 and Nd0.7Ca0.3CoO3

With a view to investigate the effect of small size of A-site cations on the magnetic properties of the rare earth cobaltates, Ln_1−xA_xCoO₃ (Ln=rare earth, A=alkaline earth), we have investigated Pr_0.7Ca_0.3CoO₃ and Nd_0.7Ca_0.3CoO₃ in detail. For this purpose, we have carried out low-field DC magnetization and ac susceptibility measurements including a study of magnetic relaxation and memory effects. Both Pr_0.7Ca_0.3CoO₃ and Nd_0.7Ca_0.3CoO₃ show frequency-dependent transitions at 70 and 55 K respectively in the ac susceptibility data, due to the onset of spin-glass like behavior. Their relaxation behavior exhibits aging effects. In addition, memory effects are found in the magnetization behavior. These characteristics establish spin-glass behavior in both these cobaltates, a behavior that is distinctly different from that of La_0.7Ca_0.3CoO₃ and La_0.5Sr_0.5CoO₃ which show well-defined ferromagnetic transitions, albeit without long-range ordering.     

Polymer-directed synthesis and magnetic property of nanoparticles-assembled BiFeO3 microrods

Nanoparticles-assembled BiFeO₃ microrods were successfully prepared via a polymer-directed solvothermal route. The phase and morphology of the products were characterized by powder X-ray diffraction (XRD), energy dispersive spectrometry (EDS), inductively coupled plasma atomic emission spectroscopy (ICP-AES), FT-IR spectroscopy and scanning electron microscopy (SEM). Experiments indicated that the linking effect originated from the interactions between polymer molecules could direct the self-assembly of building blocks into one-dimensional nanoparticles-assembled BiFeO₃ microrods. Some factors influencing the morphologies of the products were systematically investigated and a possible mechanism of the formation of the microrods was suggested. Moreover, the magnetic properties of the products were studied.     

Eu3F4S2: Synthesis, crystal structure, and magnetic properties of the mixed-valent europium(II,III) fluoride sulfide EuF2·(EuFS)2

Using the method to synthesize rare-earth metal(III) fluoride sulfides MFS (M=Y, La, Ce–Lu), in some cases we were able to obtain mixed-valent compounds such as Yb₃F₄S₂ instead. With Eu₃F₄S₂ another isotypic representative has now been synthesized. Eu₃F₄S₂ (tetragonal, I4/mmm, a=400.34(2), c=1928.17(9) pm, Z=2) is obtained from the reaction of metallic europium, elemental sulfur, and europium trifluoride in a molar ratio of 5:6:4 within seven days at 850 °C in silica-jacketed gas-tightly sealed platinum ampoules. The single-phase product consists of black plate-shaped single crystals with a square cross section, which can be obtained from a flux using equimolar amounts of NaCl as fluxing agent. The crystal structure is best described as an intergrowth structure, in which one layer of CaF₂-type EuF₂ is followed by two layers of PbFCl-type EuFS when sheeted parallel to the (001) plane. Accordingly there are two chemically and crystallographically different europium cations present. One of them (Eu²⁺) is coordinated by eight fluoride anions in a cubic fashion, the other one (Eu³⁺) exhibits a monocapped square antiprismatic coordination sphere with four F⁻ and five S²⁻ anions. Although the structural ordering of the different charged europium cations is plausible, a certain amount of charge delocalization with some polaron activity has to take place, which is suggested by the black color of the title compound. Temperature dependent magnetic susceptibility measurements of Eu₃F₄S₂ show Curie–Weiss behavior with an experimental magnetic moment of 8.19(5) μ_B per formula unit and a paramagnetic Curie temperature of 0.3(2) K. No magnetic ordering is observed down to 4.2 K. In accordance with an ionic formula splitting like (Eu^II)(Eu^III)₂F₄S₂ only one third of the europium centers in Eu₃F₄S₂ carry permanent magnetic moments. ¹⁵¹Eu-Mössbauer spectroscopic experiments at 4.2 K show one signal at an isomer shift of −12.4(1) mm/s and a second one at 0.42(4) mm/s. These signals occur in a ratio of 1:2 and correspond to Eu²⁺ and Eu³⁺, respectively. The spectra at 78 and 298 K are similar, thus no change in the Eu²⁺/Eu³⁺ fraction can be detected.     

Slow magnetic relaxation in a novel heptanuclear Dy7 cluster with five edge-sharing Dy3 triangles

A unique Dy₇ cluster with five edge-sharing Dy₃ triangles has been synthesized by incorporating the polydentate oxime ligand, 3-methyloxysalicylaldoxime, in two different binding modes in its mono- and di-deprotonated state. Both static (dc) and dynamic (ac) magnetic properties of 1 have been studied, possible single-molecule magnet behavior is observed, expanding upon the recent reports of the pure 4f type SMM.     

氟化镁锶中铕和铽的电荷迁移及其平衡解析

在氩气氛中，合成子ＳｒＭｇＦ４：ｘＥｕ，ｙＴｂ复合氟化物磷光体，该体系中Ｅｕ＾３＋和Ｅｕ＾２＋共存，随共掺入Ｔｂ浓度的增加，Ｅｕ＾３＋的荧光发射强度降低，Ｅｕ＾３＋的发光增强，并且Ｅｕ＾２＋的ＥＳＲ信号增强，认为Ｅｕ＾３＋和Ｔｂ３＋之间存在的电荷迁移，即Ｅｕ＾３＋Ｔｂ＾３＋→Ｅｕ＾２＋＋Ｔｂ＾４＋，通过半量手段研究了这一电荷迁移反应的平衡常数。     

Crystal structure and magnetic properties of the coupled spin dimer compound SrCu2(TeO3)2Cl2

Single crystals of the strontium copper tellurium oxochloride SrCu₂(TeO₃)₂Cl₂ were synthesized via solid-gas reactions in sealed evacuated silica tubes. The compound crystallizes in the monoclinic system, space group P2₁, a=7.215(2), b=7.2759(15), c=8.239(2) Å, β=96.56(4)°, Z=2. The building units are [SrO₆Cl₂] irregular polyhedra, [CuO₄] and [CuO₃Cl] square planes, [TeO₃E] tetrahedra and [TeO₃₊₁E] trigonal bipyramids; E being the 5s² lone pair of Te(IV). The Cu atoms can be regarded as forming a chain of weakly connected dimers. The magnetic susceptibility of the compound shows a broad maximum typical for antiferromagnetic spin fluctuations with a non-magnetic ground state. A Heisenberg spin model with coupled s=1/2 dimers leads to a satisfactory fitting of the experimental data.     

Electronic structure, galvanomagnetic and magnetic properties of the bismuth subhalides Bi4I4 and Bi4Br4

Two bismuth-rich subhalides, Bi₄Br₄ and Bi₄I₄, featuring extended quasi one-dimensional metallic fragments in their structures, have been investigated. The gas-phase technique of crystal growth has been refined for obtaining large (up to 5 mm long) single crystals. Electronic structure calculations on three-dimensional structures of both compounds have been performed (DFT level, hybrid B3LYP functional), predicting a semiconducting behavior for both compounds, with an indication of possible directional anisotropy of electric conductivity. Galvanomagnetic (resistance, magnetoresistance, Hall effect, thermopower) and magnetic (temperature and field dependence of magnetization) properties have been measured experimentally. Both compounds are found to be diamagnetic, room-temperature semiconductors with n-type conductivity. While Bi₄Br₄ demonstrates a typical case of one dimensionality, the difference in magnetoresistivity between Bi₄Br₄ and Bi₄I₄ indicates some weak interactions between isolated bismuth metallic fragments within the bismuth substructures.