三硫化铌高压合成与XPS分析的若干研究

 本文将报道我们在三硫化铌高压合成与相变方面的若干新的研究成果，其中包括晶体结构和电子状态以及发现特定结构的三硫化铌存在着Peierls转变的一些特征。     

Characterization of the ground state pyrene complex in ethylene-propylene copolymer solutions

Pyrene-labeled functionalized ethylene-propylene (EP) copolymer was prepared by grafting 1-pyrenebutyrylhydrazine onto EP copolymer through maleic anhydride pendants. The EP copolymer contained 60 mol % ethylene; its weight-average molecular weight (M^w) was 148,000. The pyrene-labeled amide functionalized EP copolymer, PA-EP(60/40), was made to simulate the amine functionalized EP copolymers that are commonly used as dispersant additives in motor oils. UV absorption spectra, fluorescence emission and excitation spectra, and fluorescence decay profiles of the pyrene were studied to determine the copolymer conformation and dynamics in methylcyclohexane and tetrahydrofuran (THF). The pyrene fluorescence characteristics of PA-EP(60/40) were highly dependent on the solvent. The dependence of fluorescence emission intensity on the excitation wavelength was large in methylcyclohexane and moderate in THF. A frequency shift of about 2 nm was observed between the excitation spectrum obtained with the emission line at 377 nm and that at 550 nm in the methylcyclohexane solutions, but no shift was found in the corresponding tetrahydrofuran solutions. The ratios of the preexponential factors (a₂₁/a₂₂) of the excimer decays obtained in both methylcyclohexane and THF solutions were different from ?1.0. However, the deviation of the excimer formation process from the Birks scheme is small in THF but large in methylcyclohexane. In addition, the Huggins constants obtained from intrinsic viscosity measurements of the PA-EP(60/40) copolymer solutions suggest that copolymer aggregation occurs in methylcyclohexane but not in THF. H-bonding between two pyrene-containing pendants is apparently the main driving force for the formation of the ground state pyrene complex. THF is found to be effective in inhibiting the H-bonding formation. © 1995 John Wiley & Sons, Inc.     

Osmium Complexes Useful in the Preparation of Metal Thin Film and Highly Efficient Electroluminescent Devices

Treatment of β-diketone ligand, such as hfacH (hexafluoroacetylacetone), with Os3(CO)12 in a stainless steel autoclave at elevated temperature afforded the corresponding mononuclear osmium complex [Os(CO)3(hfac)(tfa)] (1) in good yield. This complex is highly volatile and displays moderate stability at the higher temperatures; thus, it can be utilized for depositing metal thin-film material with overall quality comparable or better than those deposited using the commercially available chemical reagents. Moreover, combination of Os3(CO)12 with another class of chelate ligand such as 3-trifluoromethyl-5-(2-pyridyl) pyrazole (ppz)H gave formation of the Os(H) dicarbonyl complex [Os(CO)2(ppz)2] (2). This osmium complex shows blue phosphorescence at room temperature, which is characteristic for the 3ππ* emission with vibronic progressions at 430,457 and 480 nm. The remarkable photophysical properties were rationalized by a combination of π electron accepting CO ligand, relative ppz orientation and heavy-atom enhanced spin-orbit coupling effects. Related chemical transformations that afforded other useful luminescent Os complexes are presented.     

Dominant mode characteristics of circular groove guide

Circular groove guide is a kind of waveguide for millimeter waves with low loss, large dimensions, and low dispersion. In this paper, the dominant mode characteristics of it is analysed. The technique that mode macthing method combines with point matching method is used to derive the Nth-order characteristic equation of the guide. The 1st order, 2nd order and 3rd order approximate curves that the normalized cutoff wavelength of circular groove guide varies with c/a are given. The attenuation curves are given at 1mm, 1.5mm and 3mm wavelength. The numerical results are in well agreement with the experimental results published.Supported by National Science Foundation of P. R. China     

1,1-Insertion of substituted alkynes into the Ir-O bond of η-carboxylato iridium complexes

Alkyl-carbonyl-iridium [Ir(CH₃)(CO)(η²-O₂CR′)(PPh₃)₂]⁺ (1, R′ = CH₃, Ph, p-C₆H₄CH₃) react with alkynes (RCCH; R = Ph, p-C₆H₄CH₃) in the presence of NEt₃ to give acyl-alkynyl-iridium Ir(C(O)CH₃)(-CCR)(η²-O₂CR′)(PPh₃)₂ (4) which further react with RCCH to give alkyl-carbonyl-cis-bis(alkynyl) iridium Ir(CH₃)(CO)(CCR)₂(PPh₃)₂ (5). cis-Bis(alkenyl)iridium complexes, Ir(-CHCH₂)₂(η²-O₂CCH₃)(PPh₃)₂ (6) and (η²-O₂CCH₃)(PPh₃)₂ (7) react with substituted alkynes RCCH (R = Ph, p-C₆H₄CH₃, cyclohex-1-enyl) to give cis-bis(alkynyl) Ir(CCR)₂(η²-O₂CCH₃)(PPh₃)₂ (9) that further react with RCCH to undergo the alkyne insertion reaction into the Ir-O bond to produce iridacycles containing vinyl acetate ligands, (-CCR)₂(PPh₃)₂ (8).     

顶空-气质联用法对醋酸纤维滤棒中溶剂残留的测定

利用顶空-气质联用仪(HS/GC-MS)建立了一种同时测定醋酸纤维滤棒中溶剂残留的测定方法.利用顶空气相色谱技术,用选择离子模式对醋酸纤维滤棒中溶剂残留进行了定量分析.分析结果表明,方法线性关系良好,相关系数均大于0.998 0,检出限为0.010 4~0.157 8 mg/kg.9种溶剂残留的平均回收率为90.3%~102.2%,相对平均偏差小于10%.方法适用于醋酸纤维滤棒溶剂残留的测定且高效、准确、简便.