Hydrothermal synthesis,crystal structure and physical properties of {[Gd(H2O)4(μ2-C6NO2H5)2Gd(H2O)4](μ3-C6NO2H4)2(ZnCl3)2} · 2H2O · 2Cl

A bimetallic 4f–3d tetranuclear complex {[Gd(H₂O)₄(μ₂-C₆NO₂H₅)₂Gd(H₂O)₄](μ₃-C₆NO₂H₄)₂(ZnCl₃)₂} · 2H₂O · 2Cl (1) has been synthesized via hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Complex 1 is characterized by a tetranuclear Gd₂Zn₂ structure with the gadolinium and zinc atoms interconnected by isonicotinic acid ligands. The tetranuclear species of {[Gd(H₂O)₄(μ₂-C₆NO₂H₅)₂Gd(H₂O)₄](μ₃-C₆NO₂H₄)₂(ZnCl₃)₂} link to isolated chlorine ions and water molecules via π?π interactions and hydrogen bonds to yield a 3-D supramolecular framework. Photoluminescent investigation reveals that the title complex displays an emission in ultraviolet region. The solid-state diffuse reflectance spectra of 1 reveal the presence of a sharp optical gap of 3.66 eV.     

Syndiospecific styrene polymerization by (tert-BuC5H4)TiCl2(O-2,6-iPr2C6H3) – borate catalyst system

(^tBuC₅H₄)TiCl₂(O-2,6-ⁱPr₂C₆H₃) (2) exhibited relatively high catalytic activity for syndiospecific polymerization of styrene at 25 °C if both [PhMe₂NH]B(C₆F₅)₄ and a mixture of AlⁱBu₃/Al(n-C₈H₁₇)₃ were used as the cocatalyst. Effects of both organoaluminum and organoboron compounds were explored, and the effect of cocatalyst was different from that observed in 1-hexene polymerization catalyzed by Cp*TiCl₂(O-2,6-ⁱPr₂C₆H₃) (1). Resultant syndiotactic polystyrene possessed narrow molecular weight distribution under the optimized conditions, and the M_w values were unchanged during the time course.     

Frequency and temperature dependent electrical properties of Ni0.7Zn0.3CrxFe2−xO4 (0 ≤ x ≤ 0.5)

Series of the ferrite samples with a chemical formula Ni_0.7Zn_0.3Cr_xFe_2?xO₄ (x = 0.0–0.5) were prepared by a sol–gel auto-combustion method and annealed at 600 °C for 4 h. The prepared samples have the cubic spinel structure with no impurity phase. As the Cr³⁺ content x increases, the unit cell dimensions decrease with an increase in Cr³⁺ content x. The crystallite size is decreases from 37 nm to 21 nm as the Cr³⁺ content increases from x = 0.0 to 0.5. Resistivity increases whereas dielectric constant decreases with an increase in Cr³⁺ content x. Maxima in the dielectric loss tangent versus frequency appear when the frequency of the hopping charge carriers coincides with the frequency of the applied alternating field. Dielectric constant and dielectric loss tangent increases with increase in temperature. Saturation magnetization of sintered samples showed higher values as compared to as-prepared sample. Curie temperature deduced from AC susceptibility data decreases with increasing x.     

Crystal structure,mixture behavior,and microwave dielectric properties of novel temperature stable (1 − x)MgMoO4 − xTiO2 composite ceramics

Novel temperature stable MgMoO₄–TiO₂ microwave dielectric ceramics were prepared by a solid state reaction process at low temperature (950 °C). As TiO₂ content increases, the relative permittivity increases while the Q × f value decreases, and the variation mechanisms are proposed, respectively. The temperature coefficient of resonant frequency (τ_f) shifts to the positive direction as TiO₂ is added. The mixture mechanisms of τ_f value for two-phase composite materials are supposed. A near-zero τ_f value (3.2 ppm/°C) is obtained when x = 0.3, with ε_r = 9.13 ± 0.03 and Q × f = 11,990 GHz. The 0.7MgMoO₄–0.3TiO₂ composites are considered to be appropriate as a low temperature co-fired ceramic material for microwave wireless communication applications.     

Synthesis,structure of a coordination polymer: {Na2[Zn(C2O4)1.5H2PO4] · 2H2O}n

A phosphatooxalate compound {Na₂[Zn(C₂O₄)_1.5H₂PO₄] · 2H₂O}_n 1 was synthesized under hydrothermal condition and characterized by single-crystal X-ray diffraction, IR spectroscopy, thermal gravimetric analysis (TGA) and fluorescent spectroscopy. X-ray single-crystal analysis revealed that its structure was a new mixed inorganic–organic ligand supramolecular framework building up through multilayer assembly.     

Hydrothermal synthesis and structural characterization: a novel α-Keggin unit supported zinc-bipyridyl complex [Zn(2,2′-bipy)3]2[ZnW12O40Zn(2,2′-bipy)2] · H2O

The hydrothermal reaction of Na₂WO₄ · 2H₂O, ZnCl₂, Zn(Ac)₂ · 2H₂O, 2,2^′-bipyridine, and H₂O gives rise to a novel Keggin unit supported zinc-bipyridyl complex [Zn(2,2^′-bipy)₃]₂[ZnW₁₂O₄₀Zn(2,2^′-bipy)₂] · H₂O consisting of a novel heteropolyanion [ZnW₁₂O₄₀Zn(2,2^′-bipy)₂]⁴⁺ in which the Keggin anion [ZnW₁₂O₄₀]⁶⁻ acts as a bidentate ligand towards the transition metal cation Zn²⁺ through a terminal oxygen and a bridging oxygen from the same WO₆ octahedron.     

Low temperature sintering and microwave dielectric properties of (Mg3 − xZnx)(VO4)2 ceramics

This paper describes the effects of Zn substitution for Mg on the microwave dielectric properties of (Mg_3 − xZn_x)(VO₄)₂ ceramics. As for the XRPD patterns of (Mg_3 − xZn_x)(VO₄)₂ ceramics sintered at the sintering temperature of 750 °C, no secondary phase was detected over the whole composition range. However, in the case of the sample sintered at 850 °C, the Zn₄V₂O₉ and Zn₂V₂O₇ compounds were identified by using XRPD; this result was attributed to the decomposition of Zn₃(VO₄)₂ phase. From crystal structure analysis, it was found that the atomic distances of M(1)O (M = Mg and Zn) and M(2)O in MO₆ octahedra increased, though that of VO in VO₄ tetrahedron decreased. Moreover, the slight tilting of M(2)O₆ octahedron was observed by the Zn substitution. As for the covalency of cation–oxygen bond, the covalency of MO bond in M(1)O₆ and M(2)O₆ octahedra decreased because of the increase in the atomic distance of MO, whereas that of VO increased with increasing the Zn addition. However, as a result, the slight decrease in the covalency of cation–oxygen bond was recognized because the variation in the covalency of MO bond is predominant in this crystal structure. The dielectric constants of the samples range from 4.4 to 11.1. The decrease in the covalency may be related to the difference in the dielectric constant of each composition. The maximum Q · f value of bulk densities is effected by varying the chemical composition of (Mg_3 − xZn_x)(VO₄)₂ ceramics and it shifts toward lower sintering temperature with an increase in x within the temperature region of 800–1050 °C. The temperature coefficient of resonant frequency (τ_f) of the samples decreased with increasing of Zn, and then a variation in τ_f value was attributed to the tilting of M(2)O₆ octahedron caused by Zn substitution for Mg.     

Phase evolution and chemical durability of Zr1-xNd xO2-x/2 (0 ≤ x ≤ 1) ceramics

A series of Zr_1-xNd _xO_2-x/2 (0 ≤ x ≤ 1) ceramics was prepared by solid-state reaction method. The effects of Nd content on the phase evolution were investigated. The chemical durability of resulting waste forms was also examined. The results show that the ceramics with x < 0.1 show monoclinic and cubic zirconia phase, with 0.2 ≤ x < 0.4 exhibit a single cubic phase, with 0.4 ≤ x ≤ 0.6 exhibit a single pyrochlore phase, with 0.6 < x < 0.8 exhibit a single cubic phase and remain cubic phases and hexagonal Nd₂O₃ when 0.8 ≤ x ≤ 1. The unit cell parameters of the Nd-doped zirconia samples increase as the Nd content increases. Moreover, the normalized element release rates of Nd element in Nd-doped zirconia ceramics firstly decrease with leaching time and almost no change after 21 days (∼0⁻⁶ g m⁻² d⁻¹), demonstrating its good chemical durability.     

Novel chains constructed from heterotrinuclear units and 1,2-bis(4-pyridyl)ethane formulated as [M2M′(O2CPh)6](bpa) (M = Co,Zn, M′ = Co,Cd): Their catalytic activity

Three novel heterometallic complexes containing two bridging ligands bpa and benzoate, formulated as [M₂M′(O₂CC₆H₅]_n(bpa)_n (bpa = 1,2-bis(4-pyridyl)ethane, M₂M′ = Zn₂Co (1), Zn₂Cd (2), and Co₂Cd (3)), have been synthesized. All three compounds show one-dimensional structures containing linear heteronuclear coordination units linked by bridging bpa ligands. Reactivity study of the compounds 1–3 for the transesterification of a variety of esters has shown that they are very efficient and 2 is the best among them.     

Thermal dehydration of Y(TFA)3(H2O)3: Synthesis and molecular structures of [Y(μ,η1:η1-TFA)3(THF)(H2O)]1∞ · THF and [Y4(μ3-OH)4(μ,η1:η1-TFA)6(η1-TFA)(η2-TFA)(THF)3(DMSO)(H2O)] · 6THF (TFA = trifluoroacetate)

In order to obtain a better anhydrous precursor for various applications in materials science and catalysis, thermal dehydration reactions of Y(TFA)₃(H₂O)₃ (TFA = trifluoroacetate) (A) were investigated. Thermal treatment of A at different temperatures under vacuum (5 × 10^?2 mm) for several hours failed to give totally anhydrous yttrium trifluoroacetate (as indicated by IR). Two different complexes, a partially dehydrated [Y(μ,η¹:η¹-TFA)₃(THF)(H₂O)]_1∞·THF (1) and a partially hydrolyzed [Y₄(μ₃-OH)₄(μ,η¹:η¹-TFA)₆(η¹-TFA)(η²-TFA)(THF)₃(DMSO)(H₂O)] · 6THF (2), were obtained with good and moderate yield, respectively, by crystallization of two different thermally treated batches of A from THF (or THF + DMSO) at room temperature. More efficient dehydration of A could be achieved at 200 °C in a furnace, the obtained anhydrous yttrium tris-trifluoroacetate giving Y(TFA)₃(THF)₂ (3) on crystallization from THF. All the products were characterized by elemental analyses, FT-IR and ¹H NMR spectroscopy as well as thermo-gravimetric analysis. In addition, single crystal X-ray structures are reported for 1 and 2, which show either a terminal (η¹ and η²) or bridging (μ,η¹:η¹) bonding behavior of the TFA ligand.     

Synthesis and crystal structure of [nBu4N][Er(pic)4] · 5.5H2O: a new infrared emitter

The new erbium(III) complex of picolinic acid (Hpic), [ⁿBu₄N][Er(pic)₄] · 5.5H₂O, was synthesized and the crystal structure determined by single-crystal X-ray diffraction. The compound was further characterized using IR, Raman, ¹H NMR and elemental analysis. The picolinate ligands (pic⁻) are coordinated through N,O-chelation to the erbium cations, as shown by X-ray diffraction and spectroscopic results, leading to an eight coordinate complex. Photoluminescence measurements were performed for this compound which exhibits infrared emission.     

Synthesis and negative thermal expansion properties of solid solutions Yb2−xLaxW3O12 (0 ≤ x ≤ 2)

A new series of rare earth solid solutions Yb_2?xLa_xW₃O₁₂ were successfully synthesized by the solid-state method. Effects of substituted ion lanthanum on the microstructures and thermal expansion properties in the resulting Yb_2?xLa_xW₃O₁₂ ceramics were investigated by X-ray diffraction (XRD), thermogravimetric analyzer (TGA), field emission scanning electron microscope (FESEM) and thermal mechanical analyzer (TMA). Results indicate that the structural phase transition of the Yb_2?xLa_xW₃O₁₂ changes from orthorhombic to monoclinic with increasing substituted content of lanthanum. The pure phases can form in the composition range of 0 ≤ x < 0.5 with orthorhombic structure and 1.5 < x ≤ 2 with monoclinic one. High lanthanum content leads to a low hygroscopicity of Yb_2?xLa_xW₃O₁₂. Negative thermal coefficients of the Yb_2?xLa_xW₃O₁₂ (0 ≤ x ≤ 2) also vary from ?7.78 × 10^?6 K^?1 to 2.06 × 10^?6 K^?1 with increasing substituted content of lanthanum.