Synthesis,photophysical and electrochemical studies of di-2-pyridyl ketone complexes of rhodium(III)

Complexes of rhodium(III) with di-2-pyridyl ketone (dpk), Rh(dpk)(MeCN)Cl₃ (1) and cis-[Rh(dpk)₂Cl₂]⁺ (2), have been successfully prepared and characterized. At low temperature (77 K), complex (2) in EtOH/MeOH (4:1, v/v) shows a broad, symmetric and structureless red emission with a microsecond lifetime and, hence, is assigned as the dd* phosphorescence. Electrochemical data, including cyclic voltammetry, normal pulse voltammetry, triple pulse voltammetry and controlled potential electrolysis, have been obtained for the two dpk complexes of rhodium(III) in MeCN. On the basis of analysis of the electrochemical (1,2) and luminescence data (2), electron transfer mechanisms are proposed. For complex (1), two reduction processes occur at the metal-localized orbitals with elimination of chlorides during the first reduction step. This is followed by a one-electron reduction at the metal. For complex (2), three electrons are transferred to the metal in two successive reduction steps accompanied by elimination of two chlorides. After these two reduction steps another one-electron reduction occurs at the dpk ligand.     

手性液晶掺杂剂（S）—4‘—辛氧基—4—（2—酰氧基—丙氧基）联苯的合成

手性液晶掺杂剂（Ｓ）┐４┐辛氧基┐４┐（２┐酰氧基┐丙氧基）联苯的合成马汝建李培荣国斌＊（华东理工大学化学系上海２００２３７）关键词铁电液晶材料，手性液晶掺杂剂，合成，手征性１９９７－０２－０３收稿，１９９７－０８－０７修回铁电液晶显示器所用的材料...     

Chiral separation of 1,1'-bi-2-naphthol and its analogue on molecular imprinting monolithic columns by HPLC

Two molecular imprinting polymer (MIP) monolithic columns with (S)-(-)-1,1'-bi-2-naphthol and (R)-(+)-5,5',6,6',7,7',8,8'-octahydro-1,1'-bi-2-naphthol as the templating molecules, respectively, have been prepared by in situ polymerization using 4-vinylpyridine and ethylene dimethacrylate as functional monomer and cross-linker, respectively. The columns with good flow-through properties were obtained by changing the molar ratio of the functional monomer and the template molecule. The effects of mobile-phase composition on separation of enantiomers were systematically investigated. The results indicate that hydrophobic interaction in aqueous solution and hydrogen-bonding interaction in ACN between the enantiomers and polymers could play important roles in the retention and resolution. The effects of chromatographic conditions, such as flow rate, column temperature, sample loading, on the enantioseparation were also studied. Further, these two MIP columns show a cross-reactivity.     

<Emphasis Type="Italic">Ab initio</Emphasis> study of small coinage metal telluride clusters Au<Subscript>n</Subscript>Te<Subscript>m</Subscript> (<Emphasis Type="Italic">n,m</Emphasis> = 1, 2)

The geometries of the most stable isomers of gold telluride systems AuTe, Au₂Te, and AuTe₂ are determined using the MP2 method. The aspect of gold—telluride interaction, the electron correlation, and relativistic effects on geometry and stability are investigated at the MP2 and CCSD(T) theoretical levels. The results show that the electron correlation and relativistic effects are responsible not only for gold—gold attraction but also for additional gold—telluride interaction. The gold—telluride interaction is strong enough to modify the known pattern of bare gold clusters. Both effects are essential for determining the geometry and relative stability of this type of systems.     

PABA疏水缔合水溶性共聚物溶液的合成与性能研究

本文根据高分子的分子设计原理，合成了带苯基的疏水单体N－苯基对正丁基丙烯酰胺（BBAM）。采用自由基胶束共聚的方法制备了水溶性丙烯胺／N－苯基对正丁基丙烯酰胺（BBAM）疏水缔合型共聚物（PABA）。研究了共聚物溶液的性能及影响因素。结果表明，随共聚物溶液浓度的增加，在临界缔合浓度以上，分子间缔合大量形成，水溶液表现粘度迅速增加，表现出明显的疏水缔合行为，与HPAM相比有优异的抗盐性。     

新颍Mo-Cu-Se簇合物{MoCu3Se3I}(PPh3)3O·0.5CH2Cl2的合成及晶体结构

新颍Mo-Cu-Se簇合物{MoCu₃Se₃I}(PPh₃)₃O·0.5CH₂Cl₂是由［Et₄N］₂MoSe₄、Cu(PPh₃)₂NO₃和KI在乙腈和二氯甲烷1∶1的混合溶剂中反应所得。晶体属单斜晶系，空间群P2_{1相似文献}   

Preparation and surface properties of latexes with fluorine enriched in the shell by silicon monomer crosslinking

A series of core-shell acrylic copolymer latexes containing fluorine enriched in the shell have been prepared by emulsion polymerization of a variety of hydrocarbon monomers with (perfluoroalkyl)methyl methacrylate and vinyltriethoxysilicone. In the presence of a reactive anionic and a long chain anionic-nonionic emulsifier, the core-shell latexes were prepared and characterized by transmission electron microscopy (TEM) and tapping-mode atomic force microscopy (AFM). From AFM and contact angle measurements, it was observed that the resulting fluorine and silicon-containing acrylic copolymers with surface energy as low as 15.5 mN/m formed a dense and gradient film containing a surface layer with high a fluorine content, and that the fluorinated particles can be fixed on the surface due to the crosslinking reaction of multi-functional silicon monomer even though the fluorinated carbon number was not enough to crystallize.     

Knoevenagel condensation catalysed by poly（vinyl chloride） supported tetraethylenepentamine （PVC-TEPA）

Poly(vinyl chloride) supported tetraethylenepentamine (PVC-TEPA) has been found to be an efficient catalyst for the Knoevenagel condensation. A wide range of aromatic aldehydes easily undergo condensations with ethyl cyanoacetate and malononitrile in the commercial 95% ethanol in refluxing using PVC-TEPA as catalyst to afford the desired products of good purity in moderate to excellent yields. A recycling study confirmed that the catalyst could be reused, the yield of the desired condensation product were not reduced. The merits of this protocol are environmentally benign, simple operation, convenient work-up and good yields. Furthermore, the catalyst can easily be recovered and reused at five times with comparable yields.     

Efficient synthesis of p-bis-(chlorodifluoromethyl)benzene

Selective, high yield partial fluorination of p-bis-(trichloromethyl)benzene to p-bis-(chlorodifluoromethyl)benzene has been accomplished by warming a slurry of the p-bis-(trichloromethyl)benzene in anhydrous HF which also contains a small quantity of inert solvent, such as 1,2-dichloroethane.     

超高交联吸附树脂对芳香有机物的吸附机理

通过3种吸附树脂AmberliteXAD-4、AM-1和JX101对芳香化合物苯胺、苯酚和苯甲酸在不同温度下的吸附特征,利用前线轨道理论进行了合理解释。结果表明,吸附剂表面进行适当的修饰,可以改变吸附剂的LUMO或HOMO,使吸附质分子与吸附剂表面的功能基产生化学作用,从而产生额外的化学吸附量,为优化设计吸附剂提供了理论指导。