Structural and magnetic characterization of Mn3IrGe and Mn3Ir(Si1−xGex): experiments and theory

The structural and magnetic properties of a new ternary Ir-Mn-Ge phase, Mn₃IrGe, as well as the solid solution Mn₃Ir(Si_1−xGe_x), 0?x?1, have been investigated by means of X-ray and neutron powder diffraction, magnetization measurements and first principles calculations. The crystal structure is cubic, of the AlAu₄-type (an ordered form of the β-Mn structure), Z=4, space group P2₁3, and the unit-cell dimension varies linearly with the silicon content. For all compositions, antiferromagnetic ordering is found below a critical temperature of about 225 K. The magnetic structure is noncollinear, as a result of frustrated magnetic interactions on a triangular network of Mn atoms, on which the moments rotate 120° around the triangle axes. The magnitude of the magnetic moment at 10 K is 3.39(4) μ_B for Mn₃IrGe. The theoretical calculations reproduce with very good accuracy the magnitudes as well as the directions of the experimentally observed magnetic moments.     

真空下X2 (X=Cl、Br)与AgOCN气-固反应机理

在真空条件下完成了X2 (X=Cl、Br)与AgOCN间的气-固异相反应，利用紫外光电子能谱（PES）仪，探测与确定反应产物是XNCO (X=Cl、Br)，并推断其可能为一过渡态反应，生成中间络合物，新键产生与旧键断裂同时进行.     

Al_(70)Cu_(30)合金液态RDF高斯分解与局域结构计算

运用密度泛函B3LYP方法对AlmCun(m,n≤4)团簇结构进行量子化学计算,得到团簇的稳定构型。对不同温度下X-射线衍射实验所得的径向分布函数(RDF)在0.2～0.4nm范围内做高斯分解,结合计算结果对高斯峰的意义做了解释,认为计算所得部分团簇构型可以代表Al70Cu30合金熔体的内部局域结构。     

利用浮区法在高氧压下生长ZnO晶须

采用浮区法在高温高氧压下生长出大尺寸的ZnO晶须. X射线衍射和拉曼光谱分析结果表明, 生长的ZnO晶须结晶良好, 具有六方结构, 沿(001)方向有明显的择优生长取向. 光致发光光谱测量结果表明, 晶须在室温下有较高的紫外光致发光效率和较低的缺陷, 生长时选择大于0.3 MPa的氧压对提高IUV/Igreen有益.     

Properties of cerium-zirconium mixed oxides partially substituted by neodymium: Comparison with Zr-Ce-Pr-O ternary oxides

CeO₂ doped with praseodymium, neodymium and/or zirconium atoms were prepared by coprecipitation and by the sol-gel method. Structural properties were investigated by in situ XRD and Raman spectroscopy while oxygen storage capacity (OSC) was measured by transient CO oxidation. All the compounds, except pure Nd₂O₃, have a fluorite-type structure as well as a Raman band at 560 cm⁻¹ characteristic of the oxygen vacancies involving non-stoichiometric oxides. The lattice parameter under hydrogen, being dependent on the temperature, revealed two reduction mechanisms: one at a low temperature at the surface and another at a high temperature in the bulk. Ce-Nd binary oxides show a strong tendency towards crystallite aggregation, which reduces accessibility to gases and OSC properties. Zirconium improves the thermal resistance to sintering of both Ce-Nd and Ce-Pr oxides. The Zr-Ce-Pr-O followed by Zr-Ce-Nd-O compounds displaying high oxygen mobility at a low temperature, appear to be very promising for practical applications such as OSC materials.     

Preparation of Layer Structure-Controlled Ru-Sn-Al2O3 Catalysts and Their Reactivity

In order to achieve functional group selective hydrogenation, the layer structure of Ru-Sn-Al2O3 catalysts was controlled by using sol-gel, powder impregnation and combined sol-gel impregnation methods. The properties of the catalysts and effectiveness in hydrogenation of dimethyl terephthalate were examined. The surface Sn contents of the catalysts characterized by X-ray photoelectron spectroscopy depended on the preparation method, in spite of almost the same bulk Ru and Sn compositions measured by X-ray fluorescence analyses. TPR and CO adsorption of the catalysts also depended on the preparation method. With regard to the conversion rate of dimethyl terephthalate and the rate of product conversion from methyl 4-hydroxy methylbenzoate to p-xylene via methyl p-toluate, Ru impregnation catalysts had higher rates than the other catalysts.     

Investigations of precipitates in heat treated AgPd30/CuSn6 layers

The subject of the investigations are precipitation zones, which grew as a result of chemical diffusion in AgPd30/CuSn6 bimetals. These precipitation zones have been characterized by metallography, electron probe microanalysis and x-ray diffraction. The growth of precipitation zones in the plating layer and in the substrate layer in dependence on time have been determined. The use of x-ray diffraction alone for the identification of the precipitates could not supply satisfying results in every case. This problem was solved by the application of electron probe microanalysis using a correction method, which allows the estimation of the chemical composition of small particles.Dedicated to Professor Dr. rer. nat. Dr. h. c. Hubertus Nickel on the occasion of his 65th birthday     

Synthesis and structural, spectroscopic and magnetic studies of two new polymorphs of Mn(SeO3)·H2O

Two new manganese(II) selenite polymorphs with formula Mn(SeO₃)·H₂O have been synthesized by slow evaporation from an aqueous solution. The crystal structure of both compounds (1) and (2) have been solved from X-ray diffraction data. The structure of (1) was determined from single-crystal X-ray diffraction techniques. The compound crystallizes in the Ama2 space group, with a=5.817(1), b=13.449(3), and Z=4. The structure of (2) has been solved from X-ray powder diffraction data. This phase crystallizes in the P2₁/n space group with unit-cell parameters of a=4.921(3), b=13.121(7), , β=90.03(2)° and Z=4. Both polymorphs exhibit a layered structure formed by isolated sheets of MnO₆ octahedra and (SeO₃)²⁻ trigonal pyramids in the (010) plane. These layers, which contain one manganese and selenium atom crystallographically independent, are formed by octahedra linked between them through the selenite oxoanions. The difference of both compounds consists in the stacking of the layers along the b-axis. The IR spectra show the characteristic bands of the selenite anion. Studies of luminescence performed at 6 K and diffuse reflectance spectroscopy have been carried out for both phases. The Dq and Racah (B and C) parameters, from luminescence and diffuse reflectance spectroscopy, are Dq=705, B=750, for (1) and Dq=720, B=745, for (2). The ESR spectra of both compounds are isotropic with g-values of 1.99(1). Magnetic measurements indicate the presence of antiferromagnetic couplings in both phases. The J-exchange parameters have been estimated by fitting the experimental magnetic data to a model for square-planar lattice. The values obtained are J/k=-0.83, −0.91 K and J^′/k=-0.97, −1.20 K, for polymorphs (1) and (2), respectively.     

Mechanism of the cyclization of dimethyl diethynyl silane with selenium tetrabromide: Computational and structural studies, and monitoring

The structure of 2,4-dibromo-2-dibromomethyl-3,3-dimethyl-1-selena-3-silacyclopentene-4, formed by regioselective electrophilic addition of SeBr₄ to dimethyl diethynyl silane, has been determined using X-ray analysis technique. Quantum chemistry methods were used to study elementary stages of the reaction. It was found that the first stage consisted of SeBr₄ conversion into bimolecular complex Br₂?SeBr₂, initiated by dimethyl diethynyl silane. Possible formation of five-membered and six-membered heterocycles involves different cyclization mechanisms. The formation of only five-membered heterocycle is explained by kinetically preferable ring closure through four-center transition state. The conclusions obtained by calculations were confirmed by monitoring of the reaction using ¹H NMR method.     

Reactions of lithiated 2,5-dimethylazaferrocene with selected electrophiles

Lithiation of 2,5-dimethylazaferrocene 1 with sec-BuLi/TMEDA in THF at −78 °C proceeds (as shown by quenching with D₂O) to comparable extent on the methyl groups and the Cp ring. However, the outcome of the reaction of the lithiated 1 with an electrophile depends on the nature of this electrophile. In the reaction with 4-methoxybenzaldehyde only the product originated from the lateral lithiation is formed, whereas the reaction with 4-methoxyacetophenone and 4,4′-dimethoxybenzophenone afforded mixtures of the products resulting from lateral and ring-lithiation. Similar results were also obtained in the reaction of lithiated 1 with chlorodiphenylphosphine and diphenyl diselenide. On the other hand, the exclusive formation of the Cp-substituted product was observed in the reaction of lithiated 1 with N,N-dimethylformamide. The structures of selected products (oily compounds were transformed into the corresponding crystalline W(CO)₅-complexes) were confirmed by X-ray diffraction. The presented reactions open a novel entry to specifically substituted azaferrocenes (especially those containing heteroatom substituents) with potential applications as ligands for the homogenous catalysis.