配位聚合物{[Co(μ-4,4′-bpy)(4,4′-bpy)2·(H2O)2]·(4,4′-bipy)·(H2O)4·(OH)3·(Me)4N}n的晶体结构及性质

配位聚合物通常是通过某种有机配体与金属的配位几何选择以及无限网络的拓扑结构控制而形成的具有无限结构的化合物 [1] ,其结构新颖并具有不寻常的光电效应、非线性光学性能、磁性、超导及催化等诸多具有诱人应用前景的独特性能 .因此 ,近年来倍受化学家和材料学家的重视 [2～ 5] .以 Co为配位中心的配位聚合物若具有八面体构型 ,在一定条件下具有自旋转换能力 ,而且往往可与光电转换能力相关联 ,是一种潜在的新型信息存储材料 [6 ] .对于配位聚合物的形成 ,配体的选择最重要 . 4,4′-联吡啶及其衍生物是一种较好的刚性配体 ,相关的配位聚…     

Preparation and characterization of aliphatic/aromatic copolyesters based on 1,4-cyclohexanedicarboxylic acid

A series of biodegradable aliphatic/aromatic copolyesters, poly(butylene terephthalate)-co-poly(butylene cyclohexanedicarboxylate)-b-poly(ethylene glycol) (PTCG), were prepared by a two-step melt polycondensation method and characterized by means of GPC, FTIR, NMR, DSC, TGA, etc. The effects of aliphatic ester content on the physical, mechanical and thermal properties, as well as in vitro and in vivo degradation behaviors were investigated. The decrease in mechanical strength was observed with an increase in poly(butylene cyclohexanedicarboxylate) (PBC) molar fraction. DSC results showed one melting point and two glass transition temperatures in all samples, and the melting temperature was found to go down gradually as more cyclohexanedicarboxylic acid (CHDA) was added. During the in vitro and in vivo degradation processes, erosion of the surface was dominant as evidenced by scanning electron microscopic observations. The copolyesters containing many CHDA units were featured by the higher water uptake and faster degradation due to much richer amorphous phase within them.     

Fluoropolyethers end‐capped by polar functional groups. III. Kinetics of the reactions of hydroxy‐terminated fluoropolyethers and model fluorinated alcohols with cyclohexyl isocyanate catalyzed by organotin compounds

The kinetics of the dibutyltin dilaurate (DBTDL)‐catalyzed urethane formation reactions of cyclohexyl isocyanate (CHI) with model monofunctional fluorinated alcohols and fluoropolyether diol Z‐DOL H‐1000 of various molecular weights (100–1084 g mol^?1) in different solvents were studied. IR spectroscopy and chemical titration methods were used for measuring the rate of the total NCO disappearance at 30–60 °C. The effects of the reagents and DBTDL catalyst concentrations, the solvent and hydroxyl‐containing compound nature, and the temperature on the reaction rate and mechanism were investigated. Depending on the initial reagent concentration and solvent, the reactions could be well described by zero‐order, first‐order, second‐order, or more complex equations. The reaction mechanism, including the formation of intermediate ternary or binary complexes of reagents with the tin catalyst, could vary with the concentration and solvent and even during the reaction. The results were treated with a rate expression analogous to those used for enzymatic reactions. Under the explored conditions, the rate of the uncatalyzed reaction of fluorinated alcohols with CHI was negligible. Moreover, there was no allophanate formation, nor were there other side reactions, catalysis by urethane in the absence of DBTDL, or a synergetic effect in the presence of the tin catalyst. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3771–3795, 2002     

Co(II) Schiff碱载氧载氮性能研究

运用INDO－UHF计算方法研究了CO(Ⅱ) Schiff碱的载氧特性，结果表明，Co(Ⅱ)与O_2的作用是通过σ键组合，并具有较明显的反铁磁性耦合作用, 论证了作为第五轴向配体在可逆载氧过程中的必要性，对比研究了Co－N_2的相互作用. 计算表明，CO(Ⅱ)的Schiff碱络合物可能作为氧氮分离的活性物质，从而具有一定的、潜在的工业应用价值.     

二茂铁甲酰丙酮缩氨基硫脲金属配合物研究

将二茂铁甲酰丙酮与硫代氨基脲在水 -乙醇介质中进行缩合反应 ,得金属有机多齿配体C5H5Fe C5H4COCH2 C(CH3 ) =NNHCSNH2 (简记作 Fc TS) ,该配体分别与 d-过渡金属 [Cu( )、Co( )、Ni( )、Mn( ) ]、 B族金属 [Zn( )、Cd( ) ]及主族金属 [Pb( ) ]乙酸盐反应 ,合成了分子式为 (Fc TS) 2 M(CH3 COO) 2 的 7个新型配合物。经元素分析、IR、UV- Vis,1 H HMR、摩尔电导及固体电导的测定对配合物组成、结构、波谱性质和导电性能进行了研究。     

Thermodynamic studies of monuron

Monuron (C₉H₁₁ClN₂O; N,N-dimethyl-N′-(4-chlorophenyl) urea, CAS 150-68-5) was synthesized and the heat capacities of the compound were measured in the temperature range from 79 to 385 K with a high precision automated adiabatic calorimeter. No phase transition or thermal anomaly was observed in this range. The enthalpy and entropy data of the compound relative to the reference temperature 298.15 K were derived based on the heat capacity data. The thermodynamic properties of the compound were further investigated through DSC and TG analysis. The melting point, the molar enthalpy, and entropy of fusion were determined to be 447.6±0.1 K, 29.3±0.2 kJ mol⁻¹, and 65.4 J K⁻¹ mol⁻¹, respectively.     

Preparation and properties of rare-earth containing oxide fluoride glasses

The preparation of the rare earth containing oxide fluoride glasses LnF₃ (Ln; Y through Lu)-BaF₂-AlF₃-GeO₂ in which the nominal content of LnF₃ reached 60 mol% in maximum and their basic properties such as density, refractive index and glass transition temperature were investigated and summarized in detail. Especially, in order to discuss the local structure around the rare earth ion in the glass, the Judd-Ofelt analysis (discussion with Ω parameters) of the HoF₃-BaF₂-AlF₃-GeO₂ glasses was carried out. The unique fluorescent behavior and the magnetic properties of LnF₃-BaF₂-AlF₃-GeO₂ glasses (Ln = Tb and/or Sm) were also studied.     

A facile synthesis of solid-emissive fluorescent dyes: dialkylbenzo[b]naphtho[2,1-d]furan-6-one-type fluorophores with strong blue and green fluorescence emission properties

A new type of organic fluorophores, dialkylbenzo[b]naphtho[2,1-d]furan-6-one-type fluorophores, exhibiting strong blue and green emission in the solid state has been easily synthesized by an one-step reaction. The X-ray crystal structure demonstrated that the structural form with a chair-shape with the sterical hindered dialkyl substituents and the 9-dibutylamino group prevents the fluorophores from forming short intermolecular contacts and produces intense solid-state fluorescence emission.     

功能液晶膜的新进展

论述了功能液晶膜的新近研究结果和发展动向,指出功能液晶膜具有优异的气体分离、液体分离和电光性能,可望作为高效气体分离膜、高效液体分离膜和大面积光控膜,具有较重大的理论与实际意义。     

含二苯甲烷结构四元共缩聚杂萘聚芳酰胺的合成与性能

采用自制二胺1,2-二氢-2-(4-氨基苯基)-4-[4-(4-氨基苯氧基)-苯基]-二氮杂萘-1-酮、商品二胺4,4′-二氨基二苯甲烷和对苯二胺与对苯二甲酰氯进行低温溶液缩聚反应,改变三种二胺的比例,得到了一系列共聚酰胺树脂,其特性粘数为1·24~2·32dL/g,用FT-IR、1H-NMR手段研究了聚合物的结构;利用DSC和TGA研究了聚合物的耐热性能,结果表明,该类聚合物具有较高玻璃转化温度(301℃以上);氮气气氛中5%热失重温度在438℃以上;用一定比例的二胺制得的聚合物分别能溶于N-甲基吡咯烷酮、N,N-二甲基乙酰胺等非质子极性溶剂中并浇注得到韧性薄膜.