Site Preference of Cations and Structural Variation in MgAl2–xGaxO4 (0 ≤ x ≤ 2) Spinel Solid Solution

The crystal structures of MgAl_2–xGa_xO₄ (0 ≤ x ≤ 2) spinel solid solutions (x = 0.00, 0.38, 0.76, 0.96, 1.52, 2.00) were refined using ²⁷Al MAS NMR measurements and single crystal X‐ray diffraction technique. Site preferences of cations were investigated. The inversion parameter (i) of MgAl₂O₄ (i = 0.206) is slightly larger than given in previous studies. It is considered that the difference of inversion parameter is caused by not only the difference of heat treatment time but also some influence of melting with a flux. The distribution of Ga³⁺ is little affected by a change of the temperature from 1473 K to 973 K. The degree of order‐disorder of Mg²⁺ or Al³⁺ between the fourfold‐ and sixfold‐coordinated sites is almost constant against Ga³⁺ content (x) in the solid solution. A compositional variable of the Ga/(Mg + Ga) ratio in the sixfold‐coordinated site has a constant value through the whole compositional range: the ratio is not influenced by the occupancy of Al³⁺. The occupancy of Al³⁺ is independent of the occupancy of Ga³⁺, though it depends on the occupancy of Mg²⁺ according to thermal history. The local bond lengths were estimated from the refined data of solid solutions. The local bond length between specific cation and oxygen corresponds with that expected from the effective ionic radii except local Al–O bond length in the fourfold‐coordinated site and local Mg–O bond length in the sixfold‐coordinated site. The local Al–O bond length in the fourfold‐coordinated site (1.92 Å) is about 0.15 Å longer than the expected bond length. This difference is induced by a difference in site symmetry of the fourfold‐coordinated site. The nature that Al³⁺ in spinel structure occupies mainly the sixfold‐coordinated site arises from the character of Al³⁺ itself. The local Mg–O bond length in the sixfold‐coordinated site (2.03 Å) is about 0.07 Å shorter than the expected one. Difference Fourier synthesis for MgGa₂O₄ shows a residual electron density peak of about 0.17 e/ų in height on the center of (Ga_0.59 Mg_0.41)–O bond. This peak indicates the covalent bonding nature of Ga–O bond on the sixfold‐coordinated site in the spinel structure.     

Synthesis and properties of highly thermally stable ultrathin films of fluorine-containing hyperbranched polybenzoxazoles

In this paper, we aimed to develop ultrathin films of hyperbranched polybenzoxazole with a thickness in the range between 1 and 100 nm. They are expected to have great potential for various applications as functional materials due to their high thermal stability, good chemical resistance and mechanical strength. The synthesis of various hyperbranched poly(o-hydroxyamide)s as precursors of polybenzoxazole was examined by the polycondensation of 2,2-bis(3-amino-4-hydroxyphenyl)propane (AHP) and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (AHFP) with 1,3,5-benzenetricarbonyl trichloride (BCC), yielding the corresponding hyperbranched poly(o-hydroxyamide), poly(AHFP_m-co-AHP_n-co-BCC_2.0), with M_n in the range between 12,870 and 22,210 in satisfactory yields. Poly(AHFP_3.0-co-BCC_2.0), poly(AHFP_2.25-co-AHP_0.75-co-BCC_2.0), and poly(AHFP_1.50-co-AHP_1.50-co-BCC_2.0) showed good solubility and film-forming ability, and ultrathin films 8.9–88.6 nm thick were prepared on silicon wafers. Heating of the ultrathin films of poly(AHFP_m-co-AHP_n-co-BCC_2.0) on a hot plate at 350 °C for 1 h afforded the corresponding ultrathin films of hyperbranched polybenzoxazole, poly(AHFP_m-cyclo-AHP_n-cyclo-BCC_2.0), with a thickness of 5.3–82.4 nm. Double-layer thin films consisting of resist materials on top of hyperbranched polybenzoxazole were also prepared.     

A novel trinuclear palladium cluster compound: di‐μ3‐chloro‐tris­[chloro(tri­phenyl­phosphine‐P)­palladium] acetone solvate

The title triangular tripalladium cluster, [Pd₃­Cl₅­(C₁₈­H₁₅P)₃]·­C₃H₆O, (I), has a trigonal‐bipyramidal framework of Pd₃(μ₃‐Cl)₂, with the two Cl atoms in apical positions. Each Pd atom in the framework has two additional coordination sites to establish square‐planar cis‐PdL₂(μ₃‐Cl)₂ geometry. Three P atoms are located on the same side of the plane defined by the Pd₃ triangle, which leads to a pseudo‐C_3v symmetry for the core framework of Pd₃(μ₃‐Cl)₂P₃Cl₃. The average Pd—Cl distance trans to PPh₃ is 2.473 (8) Å, which is significantly longer than the average Pd—Cl distance of 2.294 (4) Å for those trans to terminal Cl, due to the strong trans effect of a P atom compared with a Cl atom. Compound (I) has 49 valence electrons and shows a rhombic electron‐spin resonance signal, indicating an S = ½ ground state.     

纳米孔径核孔膜的制备研究

高能硫、氪、氙离子轰击聚酯(PET)和聚碳酸酯(PC)膜后,对样品进行陈化和紫外线照射敏化.用电导法着重研究蚀刻条件对样品的归一化径迹蚀刻速率(灵敏度)的影响,结果表明优化条件下灵敏度较通用条件下提高约2倍,PET的灵敏度可达1000,PC的灵敏度可达2000,可以用于制备纳米孔径核孔膜.核孔膜中填充的铜纳米线的电镜照片显示出纳米线最小直径为20nm.用电导法计算纳米孔的孔径,该值与纳米线直径的电镜测量值在孔径大于30nm时符合良好.     

Electron cyclotron heating in high density toroidal plasmas

Wave trajectories of the ordinary mode as well as the extraordinary one injected obliquely into a magnetic field in high density toroidal plasmas, are studied theoretically. Both waves are finally converted into the electron Bernstein mode and cyclotron damped.     

Effective dephosphorylation catalyzed by fluoride ion: A novel synthesis of terminal f-alkylacetylenes from f-alkanoyl chlorides

1H-F-Alkene-1-phosphonates, easily accessible from F-alkanoyl chlorides, underwent dephosphorylation on treatment with a catalytic amount of fluoride ion at O°C to room temperature to give terminal F-alkylacetylenes in good yields.     

Synthesis of ketimines via palladium complex-catalyzed cross-coupling of imidoyl chlorides with organotin compounds

Imidoyl chlorides were successfully transformed into ketimines when treated with organotin compounds in the presence of palladium complex catalysts.     

Dehydrogenative condensation of monohydrosilanes yielding disilanes in the presence of platinum complex catalysts

Dimethylphenylsilane was catalytically dehydrogenated and condensed in the presence of platinum complexes to give 1,1,2,2-tetramethyl-1,2-diphenyl-disilane.     

On the relation of two approaches to Rubin's model of brownian particles

The relation between two approaches to Rubin's model of brownian particles is clarified. The Fokker-Planck-like equation for the model is thereby derived.     

Site equivalent all Apex 1 nm-particle of CdSe preferentially grown in solution

A 1-nm particle of CdSe showing a sharp photoabsorption peak at 350 nm has been selectively synthesized as a single species in solution. Solid NMR spectra of both atoms show a single narrow peak of large chemical shift anisotropy and asymmetry compared with the essentially isotropic bulk CdSe. This result indicates that this extremely small 1-nm particle has most of its atoms at the surface, and the atoms are deformed from the sp³ configuration of the bulk fragment into an assembly consisting entirely of apexes of equivalent symmetry that are particularly stable and preferentially grown. This observed selective stability presents the possibility of growing 1-nm particles with an atomic monostructure in macroscopic quantities.