Magnetic properties of RE2MnGe6 (RE = La,Ce) and YMn0.3Ge2 germanides

The magnetic data of RE₂MnGe₆ (RE = La, Ce) and YMn_0.3Ge₂ are reported. La₂MnGe₆ and Ce₂MnGe₆ crystallize in the orthorhombic Ce₂CuGe₆ structure type, space group Amm2 (No. 38). The non-stoichiometric YMn_0.3Ge₂ compound crystallizes with the orthorhombic CeNiSi₂-type structure (space group Cmcm (No. 36)). The studied RE₂MnGe₆ (RE = La, Ce) intermetallics are characterized by ferromagnetic properties with Curie temperatures 177 (La) and 150 K (Ce), respectively. For YMn_0.3Ge₂ the low-field magnetic measurements indicate the antiferromagnetic property below 395 K with the small ferromagnetic component. The values of the magnetic moments in the ordered state indicate the ferromagnetic ordering in La₂MnGe₆ and complex magnetic order with the ferromagnetic component in YMn_0.3Ge₂ and Ce₂MnGe₆. The hysteresis loop and values of the coercivity field indicate that these compounds are soft magnetic materials.     

Influence of rare earth cation size on the crystal structure in rare earth silicates,Na2RESiO4(OH) (RE = Sc,Yb) and NaRESiO4 (RE = La,Yb)

Crystals of Na₂ScSiO₄(OH) and Na₂YbSiO₄(OH) were synthesized at low temperatures using a sodium hydroxide based hydroflux, while crystals of NaLaSiO₄ and NaYbSiO₄ were grown at high temperatures using a sodium fluoride/sodium chloride eutectic flux. Both structure types were crystallized under reaction conditions that, when used for medium sized rare earths (RE = Pr, Nd, Sm – Tm) yield the Na₅RE₄X[SiO₄]₄ structure type, where X is OH in the hydroflux conditions and F in the eutectic flux conditions. Herein, we report the synthesis, structure, size effect, and magnetic properties of these compositions and introduce the new structure type of Na₂RESiO₄(OH), which crystallizes in the orthorhombic space group Pca2₁, of NaLaSiO₄, which crystallizes in the orthorhombic space group Pna2₁, and of NaYbSiO₄, which crystallizes in the orthorhombic space group Pnma, where both NaRESiO₄ compounds have one silicon structural analog.     

Synthesis,crystal structure and thermal behaviour of [La(hfa)3(Phen)2] (hfa = hexafluoroacetylacetonate,Phen = o-phenanthroline)

The mixed ligand complex [La(hfa)₃(Phen)₂] (I) was obtained by the interaction of La(hfa)₃ and Phen; its composition does not depend on the stoichiometry of the reagents. According to the X-ray single crystal analysis data, complex I crystallizes in the monoclinic space group P2₁/n, with a = 13.583(3) Å, b = 16.959(3) Å, c = 18.860(4) Å, β = 94.71(3)° and Z = 4. The structure of I consists of isolated mononuclear molecules, the coordination number of La being 10. Thermal behaviour and composition of the vapor phase have been studied for I by thermal analysis and mass-spectrometry using a Knudsen cell. The mixed ligand complex I was found to sublime congruently in the temperature range 370–460 K: [La(hfa)₃(Phen)₂]_(s) = [La(hfa)₃(Phen)]_(g) + Phen_(g), Δ_rH⁰(T) = 316.2 ± 1.8 kJ/mol.     

Synthesis and luminescent properties of LaInO3: RE3+ (RE = Sm,Pr and Tb) nanocrystalline phosphors for field emission displays

LaInO₃: Sm³⁺, LaInO₃: Pr³⁺ and LaInO₃: Tb³⁺ phosphors were prepared through a Pechini-type sol–gel process. X-ray diffraction, field emission scanning electron microscopy, photoluminescence, and cathodoluminescence (CL) spectra were utilized to characterize the synthesized phosphors. XRD results reveal that the pure LaInO₃ phase can also be obtained at 700 °C. FE-SEM images indicate that the LaInO₃: Sm³⁺, LaInO₃: Pr³⁺ and LaInO₃: Tb³⁺ phosphors are composed of aggregated spherical particles with sizes around 80–120 nm. Under the excitation of ultraviolet light and low voltage electron beams (1–5 kV), the LaInO₃: Sm³⁺, LaInO₃: Pr³⁺ and LaInO₃: Tb³⁺ phosphors show the characteristic emissions of Sm³⁺ (⁴G_5/2–⁶H_5/2,7/2,9/2 transitions, yellow), Pr³⁺ (³P₀–³H₄, ³P₁–³H₅, ¹D₂–³H₄ and ³P₀–³F₂ transitions, blue–green) and Tb³⁺ (⁵D₄–⁷F_6,5,4,3 transitions, green) respectively. The corresponding luminescence mechanisms are discussed. These phosphors have potential applications in field emission displays.     

Crystal chemistry and physical properties of the ternary compounds REBC (RE = Ce,Pr, Nd)

The ternary rare-earth metal boride carbides REBC (RE = Ce, Pr, Nd) were prepared by melting mixtures of the elements and subsequent annealing at temperatures between 1270 K and 1570 K. Their crystal structures were refined from single crystal X-ray diffraction data. They crystallize in the LaBC-type structure (space group P2₁2₁2₁, Z = 20); CeBC: a = 8.5021(5) Å, b = 8.5217(7) Å, c = 12.3834(7) Å, R1 = 0.033 (wR2 = 0.059) for 2838 reflections with I_o > 2σ(I_o); PrBC: a = 8.4478(5) Å, b = 8.4719(8) Å, c = 12.325(1) Å, R1 = 0.031 (wR2 = 0.063) for 2564 reflections with I_o > 2σ(I_o); NdBC: a = 8.370(1) Å, b = 8.392(1) Å, c = 12.253(3) Å, R1 = 0.035 (wR2 = 0.086) for 4275 reflections with I_o > 2σ(I_o). The structure consists of a three-dimensional framework of rare-earth metal atoms resulting from the stacking of slightly corrugated two-dimensional square nets, leading to voids filled with B₅C₅ finite chains. The magnetism of the compounds PrBC and NdBC is characterized by the onset of ferromagnetism with Curie temperatures around 10 K and 8 K, respectively. The reduced effective paramagnetic moment μ_eff ≈ 1.8 μ_B as well as the weak magnetization at 6 K, 5 T is discussed.     

Synthesis of Er5(BO3)2F9 and Properties of RE5(BO3)2F9 (RE = Er,Yb)

Er₅(BO₃)₂F₉ was synthesised under conditions of 3 GPa and 800 °C in a Walker‐type multianvil apparatus. The crystal structure was determined on the basis of single‐crystal X‐ray diffraction data, collected at room temperature. Er₅(BO₃)₂F₉ is isotypic to the recently synthesised Yb₅(BO₃)₂F₉ and crystallises in C2/c with the lattice parameters a = 2031.2(4) pm, b = 609.5(2) pm, c = 824.6(2) pm, and β = 100.29(3)°. The physical properties of RE₅(BO₃)₂F₉ (RE = Er, Yb) including high temperature behaviour and single crystal IR‐ / Raman spectroscopy were investigated.     

Critical evaluation and thermodynamic optimization of the Si-RE systems: Part I. Si-RE system (RE = La,Ce, Pr,Nd and Sm)

A critical evaluation and optimization of all available phase diagrams and thermodynamic data of the binary Si-RE (RE = La, Ce, Pr, Nd and Sm) systems were conducted to obtain reliable thermodynamic functions of all the phases in the systems. In the thermodynamic modelling, a systematic analysis involving the similarity and periodicity observed in the lanthanide series was applied to resolve inconsistencies in the experimental data and to estimate the unknown thermodynamic properties and phase equilibria data. The phase diagram of the Si-Sm system was predicted using this approach.     

Ba3MIIITiMVO9 (MIII = Fe,Ga, Y,Lu; MV = Nb,Ta, Sb) perovskite oxides: Synthesis,structure and dielectric properties

We describe the synthesis, structures and dielectric properties of new perovskite oxides of the formula, Ba₃M^IIITiM^VO₉, for M^III = Fe, Ga, Y, Lu and M^V = Nb, Ta, Sb. While M^V = Nb and Ta oxides adopt disordered/partially ordered 3C perovskite structures where M^III/Ti/M^V metal-oxygen octahedra are corner-connected, the M^V = Sb oxides show a distinct preference for the 6H structure, where Sb^V/Ti^IV metal-oxygen octahedra share a common face forming (Sb,Ti)O₉ dimers that are corner-connected to the M^IIIO₆ octahedra. The preference of antimony oxides (Sb^V:4d¹⁰) for the 6H structure – which arises from a special Sb^V–O chemical bonding that tends to avoid linear Sb–O–Sb linkages unlike Nb^V/Ta^V:d⁰ atoms which prefer ～180° Nb/Ta–O–Nb/Ta linkages – is consistent with the crystal chemistry of M^V–O oxides in general. The dielectric properties reveal a significant difference among M^III members. All the oxides with the 3C structure excepting those with M^III = Fe show a normal low loss dielectric behaviour with ε = 20–60 in the temperature range 50–400 °C; the M^III = Fe members with this structure (M^V = Nb, Ta) display a relaxor-like ferroelectric behaviour with large ε values at frequencies ≤1 MHz (50–500 °C).     

Rare earth-rich compounds RE9TMg4 (RE = Y,Dy-Tm,Lu; T = Ru,Rh, Os,Ir) with an ordered Co2Al5-type structure

The rare earth-rich intermetallic phases RE₉TMg₄ (RE = Y, Dy-Tm, Lu; T = Ru, Rh, Os, Ir) were synthesized by induction melting of the elements using sealed niobium ampoules as crucible material. The melted samples were additionally annealed in muffle furnaces and subsequently characterized by X-ray powder diffraction. The RE₉TMg₄ compounds adopt an ordered Co₂Al₅ type structure, space group P6₃/mmc. Four structures were refined from single-crystal X-ray diffractometer data: a = 953.71(5), c = 968.41(5) pm, wR2 = 0.00273, 603 F² values, 21 parameters for Tm_8.76RuMg_4.24; a = 958.37(5), c = 975.66(5), wR2 = 0.00384, 661 F² values, 20 parameters for Dy₉OsMg₄; a = 943.70(5), c = 967.91(5) pm, wR2 = 0.00430, 592 F² values, 21 parameters for Tm_8.74OsMg_4.26; a = 968.09(5), c = 978.25(5) pm, wR2 = 0.0439, 623 F² values, 21 parameters for Y_9.18IrMg_3.82. The compounds are prone to small homogeneity ranges (RE/Mg mixing). The transition metal atoms have tricapped trigonal prismatic rare earth coordination. These T@RE₉ units (TP) are condensed with empty RE₆ octahedra (O) via common triangular faces forming infinite strands with a sequence –TP–O–O–. These strands show the motif of hexagonal rod packing and they are separated by chains of edge- and corner-sharing tetrahedra. The magnesium substructures in the hexagonal Laves phase YMg₂ and the prototype Y₉CoMg₄ are structurally closely related. Charge transfer trends, electronic band structures and bonding properties were studied within DFT. The resulting picture is that cobalt brings covalent character by reducing the overall charge transfer and modifies the Laves phase YMg₂ by providing larger localization in the density of states. The Y–Co bonding in Y₉CoMg₄ prevails while weakening the Y–Mg bonds. The investigations of the magnetic properties of selected RE₉TMg₄ compounds revealed Pauli paramagnetic behavior for Y₉CoMg₄, Y₉OsMg₄ and Y₉IrMg₄. A ferromagnetic ground state with Curie temperatures of 46.0 and 47.6 K was observed for Dy₉RuMg₄ and Dy₉OsMg₄, respectively. Ho₉RuMg₄, Ho₉OsMg₄ and Tm₉OsMg₄ reveal antiferromagnetic ordering with Neél temperatures below 20 K.     

Vacuum ultraviolet spectroscopic properties of rare earth (RE) (RE = Eu,Tb, Dy,Sm, Tm)-doped K2GdZr(PO4)3 phosphate

The luminescent characteristics of RE (RE³⁺ = Eu, Tb, Dy, Sm and Tm)-doped K₂GdZr(PO₄)₃ have been investigated. The band in the range of 130–157 nm in the VUV excitation spectra of these compounds is attributed to the host lattice or PO₄^3? group absorption and the band from 157 nm to 215 nm with the maximum at 188 nm is due to the O–Zr charge transfer transition. For Eu³⁺-doped sample, the relatively weak band of O^2?–Eu³⁺ charge transfer (CTB) at 222 nm is observed and for Tb³⁺-doped sample, the band at 223 nm is related to the 4f–5d spin-allowed transition of Tb³⁺. For Dy³⁺- and Sm³⁺-doped samples, the O^2?–Dy³⁺ and O^2?–Sm³⁺ CTBs have not been observed, probably due to the 2p electrons of oxygen tightly bound to the zirconium ion in the host lattice. In Tm³⁺-doped sample, the weak O^2?–Tm³⁺ CTB is located at 170 nm. It is observed that there is energy transfer between the host and the luminescent activators (e.g. Eu³⁺, Tb³⁺ and Sm³⁺) except for Tm³⁺.     

Coupling of terminal alkynes by RuHXL2 (X = Cl or N(SiMe3)2, L = PiPr3)

The compounds RuL₂HX, where L = PⁱPr₃ and X = Cl or N(SiMe₃)₂, are catalyst precursors for dimerization of terminal alkynes to enynes and also to cumulenes at 23 °C; selectivity among these products is X-dependent, but not high. Conversion of Ru species onto the catalytic cycle was undetectably small, so alternative approaches to understanding the catalytic mechanism were employed: stoichiometric reactions, independent synthesis of candidate intermediates, and trapping with CO. These show the intermediacy of vinylidenes and vinyl compounds, and reveal conversion of cumulenes to the thermodynamically more stable enynes.     

The high-temperature heat capacity of LnPO4 (Ln = La,Ce, Gd) by drop calorimetry

The high-temperature heat capacity of three lanthanide orthophosphates of monazite structure have been measured in the temperature range (450 to 1570) K. The data have been analysed in terms of a lattice term, represented by the 4f⁰ and 4f⁷ compounds LaPO₄ and GdPO₄, and an electronic term for CePO₄. The calculated excess heat capacity thus obtained is in reasonable agreement with that calculated from the crystal field energies.     

Photocatalytic properties of CoOx-loaded nano-crystalline perovskite oxynitrides ABO2N (A = Ca,Sr, Ba,La; B = Nb,Ta)

Highly crystalline niobium- and tantalum-based oxynitride perovskite nanoparticles were obtained from hydrothermally synthesized oxide precursors by thermal ammonolysis at different temperatures. The samples were studied with respect to their morphological, optical and thermal properties as well as their photocatalytic activity in the decomposition of methyl orange. Phase pure oxynitrides were obtained at rather low ammonolysis temperatures between 740 °C (CaNbO₂N) and 1000 °C (BaTaO₂N). Particle sizes were found to be in the range 27 nm–146 nm and large specific surface areas up to 37 m² g⁻¹ were observed. High photocatalytic activities were found for CaNbO₂N and SrNbO₂N prepared at low ammonolysis temperatures. CoO_x as co-catalyst was loaded on the oxynitride particles resulting in a strong increase of the photocatalytic activities up to 30% methyl orange degradation within 3 h for SrNbO₂N:CoO_x.     

Crystal growth, structure, and physical properties of LnCu2(Al,Si)5 (Ln = La and Ce)

LnCu(2)(Al,Si)(5) (Ln = La and Ce) were synthesized and characterized. These compounds adopt the SrAu(2)Ga(5) structure type and crystallize in the tetragonal space group P4/mmm with unit cell dimensions of a ≈ 4.2 ? and c ≈ 7.9 ?. Herein, we report the structure as obtained from single crystal X-ray diffraction. Additionally, we report the magnetic susceptibility, magnetization, resistivity, and specific heat capacity data obtained for polycrystalline samples of LnCu(2)(Al,Si)(5) (Ln = La and Ce).     

Synthesis,crystal structure and luminescent properties of pyrovanadates A2CaV2O7 (A = Rb,Cs)

The novel vanadium oxides Rb₂CaV₂O₇ and Cs₂CaV₂O₇ have been prepared by solid-state reaction and their crystal structures determined and refined using X-ray, neutron powder and electron diffraction data. Rb₂CaV₂O₇ and Cs₂CaV₂O₇ are isostructural, crystallizing in space group P2₁/n with unit cell parameters: a = 13.8780(1), b = 5.96394(5), c = 10.3376(1) Å, β = 104.960(1)° and a = 14.0713(2), b = 6.0934(1), c = 10.5944(1) Å, β = 104.608(1)°, respectively. Their crystal structures can be described as a framework of CaO₆ octahedra and V₂O₇ pyrogroups with alkaline metals found in the tunnels formed. Photoluminescence (PL) and PL excitation spectra of the considered pyrovanadates have been studied in the vacuum ultraviolet (VUV) to visible light (Vis) range as well as their pulse cathode luminescence (PCL) spectra and the kinetic parameters of PCL. In the PL and the PCL spectra of both pyrovanadates recorded at T = 300 K a broad band with maxima at 2.2, 2.4 eV and two shoulders (bands) at 2.0 and 2.58 eV have been observed. At T = 10 K the band at 2.0 eV becomes the main band in the spectra. Two types of luminescence centers for each pyrovanadate, with very similar excitation bands at 3.75, 4.84, 6.2, 7.3 and 9.1 eV, have been found. The nature of the luminescence centers connected with the bands at 2.0, 2.2, 2.4 and 2.58 eV is discussed.     

Electronic structure and bonding of the hydrides Mg3TH7 (T = Mn,Re) from first principles

From pseudo-potentials and all-electrons computations within density functional theory, desorption energies within range of MgH₂ and covalent like hydrogenated intermetallic compounds are identified for hydrogen rich Mg₃TH₇, (T = Mn, Re). The rhenium based compound is found with a lower desorption energy which has been quantified from the analysis of the Bader charges within the {TH₆}^5- complex anion as related with a decreasingly ionic charge on hydrogen from Mn to Re. The electronic densities of states show insulating compounds in agreement with literature relevant to this class of salt-like hydrides with a larger band gap for the Re compound. From chemical bonding analyses stronger Mn–H bonding versus Re–H is identified in agreement with desorption energies magnitudes favoring Mg₃ReH₇.     

Synthesis,crystal structures and chemical bonding of RE5−xLixGe4 (RE = Nd,Sm and Gd; x≃ 1) with the orthorhombic Gd5Si4 type

The syntheses and single‐crystal and electronic structures of three new ternary lithium rare earth germanides, RE_5−xLi_xGe₄ (RE = Nd, Sm and Gd; x≃ 1), namely tetrasamarium lithium tetragermanide (Sm_3.97Li_1.03Ge₄), tetraneodymium lithium tetragermanide (Nd_3.97Li_1.03Ge₄) and tetragadolinium lithium tetragermanide (Gd_3.96Li_1.03Ge₄), are reported. All three compounds crystallize in the orthorhombic space group Pnma and adopt the Gd₅Si₄ structure type (Pearson code oP36). There are six atoms in the asymmetric unit: Li1 in Wyckoff site 4c, RE1 in 8d, RE2 in 8d, Ge1 in 8d, Ge2 in 4c and Ge3 in 4c. One of the RE sites, i.e. RE2, is statistically occupied by RE and Li atoms, accounting for the small deviation from ideal RE₄LiGe₄ stoichiometry.     

Influence of the RE2O3 (RE = Y,Gd) and CaO nanoadditives on the electromagnetic properties of nanocrystalline Co0.2Ni0.3Zn0.5Fe2O4

The present work reports the influence of the nanoadditives Y₂O₃, Gd₂O₃, and CaO on the magnetic, electrical and dielectric properties of sintered nanoferrites Co_0.2Ni_0.3Zn_0.5Fe₂O₄. All powders were synthesized via the polyol method. XRD analysis showed that except the nanoferrite which was obtained by in an one-post procedure, subsequent calcinations of the as-produced additives were necessary to obtain nanocrystals of the desired phases. The mean particle size inferred from TEM images of the nanoadditives sintered at 1000 °C ranges from 87 nm for Y₂O₃ to 126 nm for CaO. IR spectroscopy provided useful information on the nature of the core and the surface chemistry of the as-produced additives and their associated annealed powders. Upon sintering, it was found that the incorporation of 5 wt.% additives remarkably increased the densification of the doped materials. The most important increase in densification was observed with CaO due to its larger particles. dc M-H hysteresis loops taken at 300 K revealed a superparamagnetic behavior of the produced ferrite/nanoadditives. Additionally, as expected, the ferrite/nanoadditives showed reasonable saturation magnetization and high Curie temperature. The electrical and dielectric properties, namely the resistivity, the loss factor, and the relation frequency were found to be clearly affected by doping. The resistivity decreased with increasing temperature indicating a semiconducting behavior. Further, at room temperature, the highest resistivity was observed with Y₂O₃. The major role was attributed to the high fraction of insulating Y₂O₃ owing to its smallest particles combined with the low Fe²⁺ concentration in the ferrite nanoparticles taking advantages of the moderate sintering temperature. In addition, the dc conductivity was found to follow the Arrhenius law with a slope change observed at the Curie temperature. Further, all the additives clearly affected the ac conductivities of the pure ferrite. The variation of the dielectric permittivity with frequency and temperature was explained on the basis of M-W type of interfacial polarization. Additionally, at high frequencies, the lower dielectric loss was found with Y₂O₃ doping. It was found to be of about 10 times lower than the undoped material and much larger than reported for similar undoped bulk ferrites.