One-Pot Hydrothermal Synthesis of Two New Copper（Ⅱ） Complexes with 4-Carboxyphenoxy Acetic Acid

The one-pot hydrothermal reaction of CuCl2 with H2CPOA and 4,4＇-bpy results in two new coordination polymers, [Cu（CPOA）（4,4＇-bpy）（H2O）2]·1.5H2O （1） and [Cu2（HCPOA）4（4,4＇-bpy）4] （2） （H2CPOA=4-carboxyphenoxy acetic acid, 4,4＇-bpy=4,4＇-bipyridine） since CPOA^2- anions reach equilibrium with HCPOA^- anions in the reaction system. The crystal structure of 1 shows a triple interpenetration CdSO4-like net with 1D channel, in which lattice water molecules are located. Complex 2 is a ladder-like 1D double chain structure assembled through coordination bonds and O—H…N hydrogen bonds.     

Synthesis of a New Cobalt （Ⅱ） Complex and its Interaction with DNA

A new complex of bis(N-benzyl benzotriazole-N^3) dichloro Co(Ⅱ) (Co(Ⅱ)L2Cl2) was synthesized and its crystal was characterized. The interaction of this new complex with fs-DNA was studied by electrochemical and UV spectrophotometric method. In 0.01 mol/L pH 4.2 Tris-HCl buffer solution Co(Ⅱ)L2Cl2 has two reductive peaks with peak potentials at 0.38 V and 0.27 V, respectively, and an oxidative peak at 1.05 V. After the addition of DNA, the peak currents decrease and the peak potential at 0.27 V shifts negatively. The UV spectrophotometric experiment indicates that the maximum absorbance of Co(Ⅱ)L2Cl2 at 204 nm decreases and exhibits bathochromic shift after the addition of DNA. All the results reveal that Co(Ⅱ)L2Cl2binds with DNA by intercalation as well as electrostatic interaction.     

Synthesis, Characterization, Spectroscopic and Electrochemical Properties of New Mono- and Binuclear Copper（Ⅰ） Complexes with Substituted 2,2′-Bipyridine

The mono- and binuclear Cu(Ⅰ) complexes with substituted 2,2′-bipyridine and iodide ligands, [CuL2]BF4(L=4-methoxycarbonyl-6-(4-methylphenyl)-2,2′-bipyridine (a), 6-(4-hydroxymethylphenyl)-2,2′-bipyridine (b) and 6-(4-methoxylphenyl)-2,2′-bipyridine (c)) and [Cu2(μ-I)2L2] were prepared, and the crystal structures of the complexes were obtained from signal-crystal X-ray diffractional analysis. The spectroscopic properties of the complexes in dichloromethane are dominated by low energy MLCT bands from 360 to 650 nrn. The electrochemical studies of mononuclear complexes reveal that the complexes have stable copper(Ⅰ) state.     

Synthesis of New Multibranch Chromophores with Strong Light-emitting in Solution and in PMMA Film

Three new chromophores with triphenylamine as molecular focal point bearing one,two, or three 4-(n-butyloxystyryl) group(s) at the periphery respectively, (named as T1, T2, and T3) have been synthesized and characterized. It is interesting to find that the fluorescence quantum yield increases from T1 (0.489), to T3 (0.535), and to T2 (0.628) in cyclohexane, meanwhile the lifetime for T3 is shorter than T1 and T2, which is an important characteristic for applications in light emitting diode. Also PMMA (polymethyl methacrylate) film doped with T3 gives stronger fluorescence than T1, and T2. Cyclic voltammetry showed that T3 exhibited lowest oxidation potential of-0.52 V vs SCE, suggesting its better hole-transport property.     

Syntheses, Characterization and Crystal Structures of New Nickel Complexes with 2,6-Bis （ imino ） pyridyl Ligands

In the past decade, the imino-complexes based on late transition metal have received significantly increasing attention for their excellent performance in the olefin polymerization area since Brookhart et al. demonstrated that the Ni( Ⅱ ) complexes incorporating with sterically hindered α-diimine ligands could be used in the polymerization of ethylene to form high molecular weight polymers.     

Two Novel Copper （ Ⅱ ） Complexes with A Novel Ligand 2,4-Di （2-aminopyridine）- 6-methylpyrimidine

Introduction The design and syntheses of multidentate Ndonor ligands have become the focus of much interest in the chemical field^[1-4] because these ligands can form multinuclear metal compounds, coordination polymers and supramolecular compounds, which play a very important role in the biological systems, magnetic materials, electric materials,     

Synthesis and Chromatographic Properties of New β-Cyclodextrin Derivatives with α-Schiff Base Groups for HPLC

β-Cyclodextrin 1 was directly oxidized to the corresponding monoaldehyde 2 on their primary faces by cyclized 2-iodoxybenzoic acid(IBX) in DMSO, followed by the synthesis of β-cyclodextrin derivatives bearing Schiff-base group 3. A new chiral stationary phase(BCDS 6) was then prepared by immobilization of β-cyclodextrin derivative with α-Schiff base group onto the surface of sillica gel. A series of compounds with amino groups were readily separated using this CSE Methanol and acetonitrile were tested as the mobile phase while the influence of temperature and the addition of aqueous triethylammonium acetate buffer to the mobile phase was also innvestigated. Ferrocene ligand with Schiff-based groups have been separated satisfactorilly on BCDS column.     

Synthesis and Thermal Crosslinking Behavior of Poly（aryl ether ketone）s Containing 1,4-Naphthalene Moieties

A new monomer, 1,4-bis(4-fluorobenzoyl) naphthalene (compound 2) was synthesized via a two-step reaction. 1,4-Naphthalenedicarboxylic acid chloride (compound 1) was prepared by using the acyl chlorization reaction of 1,4-naphthalenedicarboxylic acid with thionyl chloride. The Friedel-Crafts acylation of compound 1 with fluorobenzene afforded compound 2 in a 80% yield. The polycondensation of compound 2 with various bisphenols in tetramethylene sulfone(TMS) in the presence of excess potassium carbonate as a condensation reagent was carried out at 210℃ to quantitatively afford the corresponding poly(aryl ether ketone)s (compounds 3-8) containing 1,4-naphthalene moieties. Thermal analyses showed that the polymers have Tg values ranging from 496 to 500 K and are thermally stable in air with initial mass loss above 500℃. These novel polymers exhibited an excellent solubility in organic solvents including NMP, DMAc, and chloroform, etc. In addition, the glass transition temperatures of these polymers increased and the polymers became insoluble in chloroform after treated at 260℃, indicating the occurrence of a thermal crosslinking reaction.     

Synthesis and Thermal Rearrangement of Tetramethyldisilane-bridged Bis(cyclopentadienyl) Diiron Complexes with Bis(phosphine)Substitution

Photolysis of [Me2SiSiMe2)[C5H4Fe(CO2)]2with a series of bis(phosphine)ligands Ph2P(CH2)n PPh2(n=1-4) leads to the formation of the corresponding diiron complexes with intramolecular and intermolecular bis(phosphine) substitution.When these complexes were heated in refluxing xylene.only in the complexes with intermolecular bis(phosphine )substitution the thermal rearrangement reaction occurred.     

The Thermal Stability of Ciprofloxacin Complexes with Magnesium(II), Zinc(II) and Cobalt(II)

The thermal behaviour of Mg(II), Zn(II) and Co(II) compounds of ciprofloxacin was studied by thermogravimetry (TG) and differential thermal analysis (DTA) in order to determine or to confirm some structural characteristics of substances. The complexes decompose in two steps: dehydration and pyrolytic decomposition of the anhydrous complexes to form metal oxide or metal fluoride. The dehydration process of one magnesium(II) compound takes place in two steps suggesting a marked difference in the bonding of water molecules. The different bonding mode of the ciprofloxacin molecules in both magnesium compounds leads to different residues of the thermal decompositions. This revised version was published online in August 2006 with corrections to the Cover Date.     

The Thermal Decomposition of Magnesium(II) Complexes with Acetic and Halogenacetic Acids

Thermogravimetry (TG), differential thermal analysis (DTA) and other analytical methods have been applied to the investigation of the thermal behaviour and structure of the compounds Mg(Ac)₂ × 2H₂ O(I), Mg(ClAc)₂ ×2H₂ O(II) and Mg(Cl₂ Ac)₂ ×H₂ O(III) (Ac =CH₃ COO⁻ , ClAc =ClCH2COO⁻ , Cl ₂ Ac =Cl₂ CHCOO⁻ ). The solid phased intermediate and resultant products of thermolysis had been identified. The possible scheme of destruction of the complexes is suggested. The halogenacetato magnesium complexes (II–III) are thermally more stable than the acetatomagnesium complex I. The final products of the decomposition of compounds were MgO. Infrared (IR) data suggest to a unidentate coordination of carboxylate ions to magnesium ions in complexes I–III. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis and Thermal Study of the Barium Complexes with 8-hydroxyquinolinate Derivatives

In this present work, barium ion was reacted with different ligands which are 5,7-dibromo 5,7-dichloro, 7-iodo and 5-chloro-7-iodo-8-hydroxyquinoline, in acetone/ammonium hydroxide medium under constant stirring and the obtained compounds were as follows: (I) Ba[(C₉ H₄ ONBr₂ )₂ ]⋅1.5H₂ O; (II) Ba[(C₉ H₄ ONCl₂ )(OH)]⋅1H₂ O; (III) Ba[(C₉ H₅ ONI)₂ ]⋅1H₂ O and (IV) Ba[(C₉ H₄ ONICl)₂ ]⋅5H₂ O, respectively. The compounds were characterized by elemental analysis, infrared absorption spectrum (IR), inductively coupled plasma spectrometry (ICP), simultaneous thermogravimetry-differential thermal analysis (TG-DTA) and differential scanning calorimeter (DSC). The final residue of the thermal decomposition was characterized as orthorhombic BaBr₂from (I); the intermediate residue, as a mixture of orthorhombic BaCO₃ and BaCl₂ and cubic BaO and the final residue, as a mixture of cubic and tetragonal BaO and orthorhombic BaCl₂ (II); the intermediate residue, as orthorhombic BaCO₃ and as a final residue, a mixture of cubic and tetragonal BaO from (III); and the intermediate residue, as a mixture of orthorhombic BaCO₃ and BaCl₂ and as a final residue, a mixture of cubic and tetragonal BaO and orthorhombic BaCl₂ from (IV). This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal Studies on Solid Complexes of Saccharin with Divalent Transition Metal Ions

The thermal decompositions of Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes of saccharin were studied in static air atmosphere. All of the complexes contain four molecules of coordination water and two molecules of crystallization water. The water molecules were removed in a single stage, except from the Zn(II) complex, which exhibited two endothermic effects. The dehydration process was usually accompanied by a sharp colour change. The anhydrous complexes exhibited a phase transition and the decomposition or combustion of saccharin occurred in the second and subsequent stages. The final decomposition products were identified by XRPD as the respective metal oxides. The kinetic parameters, such as the order of reaction and energy of activation for the dehydration stage, were evaluated and the thermal stabilities of the complexes are discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

过氧铌杂多钨酸盐热分解动力学参数的测定

钼和钨的杂多配合物由于其高催化活性及抗病毒性吸引着人们的关注［１］。杂多配合物的组成改变能调变其酸性、氧化性、反应性等,因此,混配型杂多配合物的研究近二十年来十分活跃。铌取代的杂多配合物在催化方面具有很独特的性质,其催化的工业应用及其机理已引起广泛的兴趣［２］。我们发现,过氧铌杂多配合物比非过氧杂多配合物具有更高的催化活性［３］。杂多酸盐的热稳定性是影响多相催化活性的重要性质,迄今有关过氧杂多配合物的热性质和热分解反应动力学参数的研究未见报道。本文用ＴＧ、ＤＴＡ、ＤＳＣ溶解度试验,变温红外和Ｘ一…     

Thermal Behaviour of Oxovanadium(IV) Complexes of Halogenated Derivatives of 8-hydroxyquinoline

The thermal behaviour of a series of oxovanadium(IV) complexes of halogenated derivatives of 8-hydroxyquinoline was investigated by means of TG and DTA measurements in oxygen atmosphere. V₂O₅ was the final pyrolysis residue in all cases.This revised version was published online in November 2005 with corrections to the Cover Date.     

Thermal BEHAVIOR of the Ti(IV), Zr(IV) and Pb(II) Complexes with 5-nitro-8-hydroxyquinoline

Ti(IV), Zr(IV) and Pb(II) complexes with 5-nitro-8-hydroxyquinoline (5-NQ) were obtained by precipitation in acetone/ammonium solution medium. The compounds TiO(C₉H₅N₂O₃)2·;0.5H₂O, ZrO(C₉H₅N₂O₃)₂·₂H₂O and Pb(C₉H₅N₂O₃)₂ were characterized by Elemental Analysis, X-ray Diffratometry and Infrared Absorption Spectrometry and their thermal behavior followed by TG/DTA. This present study intends to show the variations in the thermal behavior of the compounds and in the composition and/or structure of final oxide residues, in different atmospheres and heating rates. This revised version was published online in July 2006 with corrections to the Cover Date.     

Keggin型杂多酸铯盐催化苯羟基化反应

采用室温固相法制备了具有Keggin结构的杂多酸铯盐催化剂(Cs_xH_3+n-xPMo_12-nV_nO₄₀, n＝0, 1, 2, x＝0.5～3.0). 红外、X射线粉末衍射及循环伏安技术研究显示, 钒取代钼原子可提高催化剂的氧化还原性, 铯取代数的增加可提高催化剂的疏水性但降低氧化还原性. 在H₂O₂为氧化剂的苯羟基化反应中, 随着铯取代数目的增加, 催化剂的溶脱情况得到明显改善. 在氧化还原性和疏水性协同作用下, Cs₂H₃PMo₁₀V₂O₄₀在Cs_xH_3+n-xPMo_12-nV_nO₄₀系列催化剂中显示出相对最佳的苯羟基化催化活性(苯酚收率19.2%)和重复使用性能.     

Thermal Decomposition of Mg(II) Complexes with Ronicol

The thermal decomposition of the complexes Mg(Clac)₂ (ron)₂ ×3H₂ O(I), Mg(Cl₂ ac)₂ (ron)₂ ×3H₂ O(II) and Mg(Cl₃ ac)₂ (ron)₂ ×3H₂ O(III), where Clac =ClCH₂ COO^- , Cl ₂ ac =Cl₂ CHCOO^- , Cl ₃ ac =Cl₃ CCOO^- and ron =3-pyridylcarbinol (ronicol) had been investigated in air atmosphere in temperature range 20–1000°C by means of TG and DTA. The composition of the complexes and the solid state intermediate and resultant products of thermolysis had been identified by means of elemental analysis and complexometric titration. The possible scheme of destruction of the complexes is suggested. The final product of the thermal decomposition was MgO. The thermal stability of the complexes can be ordered in the sequence: I<III<II. IR data suggest that ronicol was coordinated to Mg(II) through the nitrogen atom of its heterocyclic ring. This revised version was published online in July 2006 with corrections to the Cover Date.     

杂多酸催化松香裂解产物中非挥发性油成分分析

杂多酸 (HPA)可有效催化松香的裂解 ,其主产物为中性、非挥发性油状物。文章利用气相色谱 /质谱 (GC/MS)联用技术对该产物成分进行了分析 ,共分离出 67个峰 ;通过与数据库标准图谱进行对照 ,鉴定出了绝大部分化合物 ;其中 2 1种化合物含量较高 ,占油状物总含量的 88.2 3 % ,主要是由松香裂解和氧化产生的环烯烃、芳香烃和芳香酮等。