Luminescence properties of efficient X-ray phosphors of YBa3B9O18, LuBa3(BO3)3, α-YBa3(BO3)3 and LuBO3

The samples of YBa₃B₉O₁₈, LuBa₃(BO₃)₃, α-YBa₃(BO₃)₃ and LuBO₃ powders have been synthesized by the solid-state reaction methods at high temperature and their X-ray excited luminescent properties were investigated. All the studied materials show a broad emission band in the wavelength range of 300-550 nm with the peak centers at about 385 nm for YBa₃B₉O₁₈ and LuBa₃(BO₃)₃, 415 nm for α-YBa₃(BO₃)₃ and 360 nm for LuBO₃ powders, respectively. Even though those compounds have the different atomic structures, they have the common structural feature of each yttrium or lutetium ion bonded to six separate BO₃ groups, i.e., octahedral RE(BO₃)₆ (RE=Lu or Y) moiety. This octahedral RE(BO₃)₆(RE=Lu or Y) moiety seems to be an important structural element for efficient X-ray excited luminescence of those compounds, as are the edge-sharing octahedral TaO₆ chains for tantalate emission.     

稀土（Nd,Pr）（Ⅲ）双酞菁衍生物的合成,表征和气敏特性

合成了八－４－（四氢糖氧基）酞菁钕（Ⅲ）（Ａ）、八－４－（β－萘氧基）酞菁钕（Ⅲ）（Ｂ）、八－４－（２，４－二叔戊基苯氧基）酞菁钕（Ⅲ）（Ｃ）和八－４－（２，４－二叔戊基苯氧基）酞菁镨（Ⅲ）（Ｄ）４种新的稀土（Ｎｄ、Ｐｒ）（Ⅲ）双酞菁衍生物，经元素分析、红外光谱、核磁共振谱表征。紫外可见光谱表明，它们在氯仿（１０＾－６ｍｏｌ／Ｌ）溶液中以单分子形式存在。热重分析证明配合物的热稳定性：Ｂ＞Ｃ￣Ｄ＞Ａ     

“Constrained geometry” catalysts of the rare-earth metals for the hydrosilylation of olefins

A series of yttrium and lutetium alkyl complexes [Ln(η⁵-C₅Me₄ZNR′-κN)(CH₂SiMe₃)(THF)_n] (Ln = Y, Lu) was prepared by reacting the tris(trimethylsilylmethyl) precursor [Ln(CH₂SiMe₃)₃(THF)₂] with different linked amino-cyclopentadienes of the type (C₅Me₄H)ZNHR′ (Z = SiMe₂, CH₂SiMe₂; R′ = tBu, Ph, C₆H₄-tBu-4, C₆H₄-nBu-4). The catalytic activity of these alkyl complexes in the hydrosilylation of 1-decene and styrene using PhSiH₃ as reagent was examined under standard conditions. A significant influence of the ligand structure on the catalytic property (turnover frequency, regioselectivity) was observed with the yttrium complex [Y(η⁵-C₅Me₄CH₂SiMe₂NtBu-κN)(CH₂SiMe₃)(THF)] being the most active for 1-decene hydrosilylation.     

Preparation and crystal structure of ternary rare-earth platinum metal aluminides R2T3Al9 (T=Rh, Ir, Pd) with Y2Co3Ga9-type structure and magnetic properties of the iridium compounds

The ternary aluminides R₂Rh₃Al₉ (R=Y, La-Nd, Sm, Gd-Tm, Lu), R₂Ir₃Al₉ (R=Y, La-Nd, Sm, Gd-Lu), and R₂Pd₃Al₉ (R=Y, Gd-Tm) have been prepared by arc melting of the elemental components with an excess of aluminum and dissolving the aluminum-rich matrix in hydrochloric acid. They crystallize with Y₂Co₃Ga₉-type structure: Cmcm, Z=4. The crystal structures of Ho₂Rh₃Al₉ and Er₂Ir₃Al₉ have been refined from single-crystal X-ray data; Ho₂Rh₃Al₉: a=1316.8(3) pm, b=760.2(2) pm, c=933.7(2) pm, R=0.044 for 255 structure factors and 27 variables; Er₂Ir₃Al₉: a=1313.8(2) pm, b=758.5(1) pm, c=933.8(2) pm, R=0.057 (392 F values, 27 variables). The structure may be viewed as consisting of atomic layers of the compositions A=R₂Al₃ and B=T₃Al₆ which alternate in the sequence ABAB along the z direction. Approximately 33% and 27% of the A layers were found to be misplaced in the crystals investigated for Ho₂Rh₃Al₉ and Er₂Ir₃Al₉, respectively. The magnetic properties of most iridium-containing compounds have been determined with a superconducting quantum interference device magnetometer. The yttrium and the lanthanum compounds show Pauli paramagnetism, others reflect the magnetic behavior of the rare-earth components. The magnetic ordering temperatures are all lower than 20 K.     

Magnetic and calorimetric studies on rare-earth iron borates LnFe3(BO3)4 (Ln=Y, La-Nd, Sm-Ho)

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.     

Synthesis, structure, and physical properties of Ce2PdGa10

A new ternary compound, Ce₂PdGa₁₀, has been synthesized using Ga flux and characterized by single-crystal X-ray diffraction. Ce₂PdGa₁₀ adopts a tetragonal structure in the I₄/mmm space group and is isostructural to Ce₂NiGa₁₀. Lattice parameters are , , , and Z=2. The compound is metallic (dρ/dT>0), with the resistance decreasing roughly linearly with temperature from 300 to 175 K. The magnetic susceptibility of Ce₂PdGa₁₀ is consistent with local-moment paramagnetism and no long-range magnetic ordering occurs down to 2 K. A large positive magnetoresistance over 200% is observed at 2 K for fields of 9 T. In this paper, we present the structure and physical properties of Ce₂PdGa₁₀ and compared them to CePdGa₆.     

RING-OPENING POLYMERIZATION OF ε-CAPROLACTONE BY LANTHANOCENE CATALYSIS*

Ring-opening polymerization of ε-caprolactone (CL) catalyzed bylanthanocenes, O(C_2H_4C_5H_3CH_3)_2YCl (Cat-YCl) and Me_2Si[(CH_3)_3SiC_5H_3]_2NdCl(Cat-NdCl) has been carried out for the first time. It has been found that both yttroceneand neodymocene are very efficient to catalyze the polymerization of CL, giving high molec-ular weight poly (ε-caprolactone) (PCL ). The effects of [cat] / [ε- CL] molar ratio, polymeriza-tion temperature and time, as well as solvents were investigated and polymerization tem-perature is found to be the most important factor affecting the polymerization. The bulkpolymerization gives higher molecular weight PCL and higher conversion than that in solu-tion polymerization. NaBPh_4 was found to promote the polymerization of ε-caprolactone,and thus to increase both the polymerization conversion and MW of poly (ε- caprolactone ).     

4,4′-Dipyridyl complexes of rare-earth thiocyanates

4,4-Dipyridyl complexes of rare-earth thiocyanates of the formulaLn(4-dipy)₂(NCS)₃·5H₂O (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, 4-dipy = 4,4-dipyridyl) have been synthesized. The IR spectra of these compounds and other physical properties are discussed. The thermal decomposition of some compounds (in the order Gd ÷ Lu) has been investigated.

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4,4-Dipyridylkomplexe von Seltenerdmetallthiocyanaten

Zusammenfassung Es wurden 4,4-Dipyridylkomplexe des TypesLn(4-dipy)₂(NCS)₃·5H₂O mitLn = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu und Y dargestellt. Die IR-Spektren und andere physikalische Eigenschaften werden diskutiert und die thermische Zersetzung von einigen Verbindungen (in der Reihe Gd ÷ Lu) untersucht.

     

Edge-Defined Film-Fed (EFG) Growth of Rare-Earth Orthovanadates REVO4 (RE=Y,Gd): Approaches to Attain High-Quality Shaped Growth

In spite of their superior laser and polarizer properties rare-earth orthovanadates (REVO₄) single crystals have not been adopted yet into extensive industrial applications because of crystal growth difficulties. The main problems of CZ technique are compositional change and diameter instability. This work presents the first attempt to apply the edge-defined film-fed growth (EFG) technique by which well-shaped REVO₄crystals have been grown directly. The capillary properties of YVO₄ and GdVO₄ melt have been measured. The applicability of shaped growth for rare-earth orthovanadate family was approved by successful EFG growth of transparent rod-like macro-defect-free single crystals of YVO₄ and GdVO₄. We address two main approaches to enhance the quality of EFG crystals: (i) meniscus and crystal shape stability dependence on die top shape and (ii) the strategy of effective operating control. Concave die top was found to be the best choice for high-quality EFG growth of REVO₄ along [001] direction. The spectral analysis of weight signal from growing crystal was shown to be a useful feedforward clue to prevent crystallinity degradation at a very early stage. A reasonable stability of the EFG process was achieved using [211], [101], [001] and [100] pulling directions.     

Synthesis,Characterization, and Crystal Structure of Na3B20, determined and refined from X‐ray and Neutron Powder Data

At 1050 ?C boron combines with sodium forming a boride of formerly unknown composition and crystal structure. The investigation of the homogeneous, monophasic, and crystalline powder was performed using X‐ray (23 ?C) and neutron (–271.5 ?C) diffraction methods. The structure solution led to an unusual arrangement of boron atoms, characterized by two different types of polyhedra, a distorted pentagonal bipyramid and a distorted octahedron. The Rietveld refinement of the crystal structure was carried out in the orthorhombic space group Cmmm (X‐ray: a = 18.6945(6) Å, b = 5.7009(2) Å, c = 4.1506(1) Å, V = 442.35(1) ų, Z = 2; R_wp = 0.087, R_p = 0.067).