Syntheses and spectroscopic studies on zinc(II) and mercury(II) complexes of isatin-3-thiosemicarbazone

Zinc(II) and mercury(II) complexes were prepared by reacting isatin-3-thiosemicarbazone (ISTSCH) with zinc(II) acetate or mercury(II) bromide. The complexes were characterized by IR, Raman, diffuse reflectance, ¹H and ¹³C NMR spectra and elemental analysis. Tetrahedral structures for Zn(ISTSC)₂ and Hg(ISTSCH)Br₂ are suggested.     

基于松香酸酐的环氧树脂体系固化动力学及TTT图绘制

研制了基于松香酸酐固化剂的生物质环氧树脂体系,采用全动态DSC法研究了树脂体系的固化反应动力学,通过半经验的唯象模型拟合得到了固化反应参数,活化能Ea为59.68 kJ/g,指前因子A0为1.28×1015s-1,反应级数n为2.483,由此建立了体系固化温度/时间/固化度间的关系;采用恒温DSC及DMA方法测试玻璃化转变温度,应用DiBenedetto经验方程拟合得到了玻璃化转变温度与固化度间的关系.应用锥板旋转黏度计测试了树脂体系不同温度下的凝胶时间,通过线性回归分析得到了凝胶时间与温度之间的关系.由唯象模型和DiBenedetto方程分别计算得到凝胶时的固化度为0.386,玻璃化转变温度为26.22°C.由上述工作绘制了基于松香酸酐生物质树脂体系的TTT(time-temperature-transition diagram)固化图,可确定树脂体系在不同温度任意时间下的状态.     

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.     

端噁唑啉聚醚对环氧树脂的固化与增韧作用的研究

用IR、DSC等分析方法研究了端2-噁唑啉聚环氧丙烷(活性聚醚)与环氧树脂的固化反应,对固化机理作了讨论。并考察了不同分子量活性聚醚对环氧树脂的增韧作用。结果表明,此活性聚醚对环氧树脂增韧效果明显,固化树脂综合性能较好。     

Synthesis and Thermal Decomposition of Mixed 2,4'-bipyridine-oxalato Complexes With Mn(II), Co(II), Ni(II) and Cu(II)

The mixed 2,4'-bipyridine-oxalato complexes of the formulae M(2,4'-bipy)₂ C₂ O₄ 2H₂ O (M (II)=Mn, Co, Ni, Cu; 2,4'-bipyridine=2,4'-bipy or L ; C₂ O^2– ₄ =ox) have been prepared and characterized. IR data show that the 2,4'-bipy coordinated with these metals(II) via the least hindered (4')N atom; that oxalate group acts as bidentate chelating ligand. Room temperature magnetic moments are normal for the orbital singlet states. The thermal decomposition of these complexes was investigated by TG, DTA and DTG in air. The endothermic or exothermic character of the decomposition of ML₂ (ox)2H₂ O was discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Spectral and structural studies of Ni(II) and Zn(II) complexes of N-trans-cinnamylidene-2-mercaptoaniline

Ni(II) and Zn(II) complexes of the bidentate thiol ligand N-trans-cinnamylidene-2-mercaptoaniline which is obtained from trans-cinnamaldehyde and 2-mercaptoaniline were prepared and characterized by their IR absorption spectra, X-ray powder diffraction measurements, elemental analysis and ¹H-NMR spectra. On the other hand, energy minimization studies of the molecules were carried out to obtain the most probable three-dimensional molecular conformations.The comparative ¹H-NMR, IR, X-ray powder diffraction and energy minimization studies have shown that metal atoms are connected to the N and S atoms of Schiff bases and the complex have cis type fashion.     

Preparation and Thermal Decomposition of Copper(II) Complexes with 4-Methylimidazole

Simple and mixed compounds of the formulae Cu(4-Meim)₂, CuSal(4-Meim), CuSal(4-Meim)₂ and CuSalox(4-Meim)₂, where 4-Meim=4-methylimidazole, Sal=(OC₆H₄COO)²⁻, Salox=(OC₆H₄CHNO)²⁻ have been prepared. Thermal decomposition reactions have been established on the basis of thermal and X-ray analyses of these compounds. The pyrolysis proceeds in several (3–4) stages connected with the mass loss and exothermic effects. As a result of the last stage of decomposition CuO is formed. This revised version was published online in August 2006 with corrections to the Cover Date.     

N16-oxides of sparteine, 2-methylsparteine and 2-phenylsparteine as ligands; spectroscopic and DFT studies of complexes with ZnX2 (X=Cl,Br)

Six new ZnX₂ (X=Cl, Br) complexes with N16-oxides of sparteine, 2-methylsparteine and 2-phenylsparteine as ligands have been synthesized and characterized by MS, IR, NMR and DFT methods. All complexes have 1 : 1 stoichiometry. Complexation with N16-oxides involves inversion of the configuration at N16, converting ring C from a boat into a chair with the oxygen engaged in coordination. All complexes investigated are of composition [(L–H)⁺(ZnX₃)^?] (where L is N-oxide). The structures of the complexes obtained have been compared with those of the monoperchlorate salts of the N-oxides.     

Homo‐ and Heterodinuclear Helicates of Lanthanide(III), Zinc(II) and Aluminium(III) Based on 8‐Hydroxyquinoline Ligands

Homonuclear helicates with rare‐earth‐metal(III) ions or heteronuclear derivatives with rare‐earth‐metal and aluminium or zinc centres are obtained in alkali‐metal‐templated self‐assembly processes from isobutenylidene‐bridged homoditopic bis(2‐carbamido‐8‐hydroxyquinoline)‐derived ligands 1 ? H₂ and 2 ? H₂ or heteroditopic (8‐hydroxyquinoline)(2‐carbamido‐8‐hydroxyquinoline)‐derived ligands 3 ? H₂ and 4 ? H₂. Diamagnetic coordination compounds possess a high stability in organic solvents such as CDCl₃, [D₄]MeOH or [D₆]DMSO and can be well characterised by ¹H NMR spectroscopy by using methylene protons and the protons of the vinylic units of the ligand as stereochemical or symmetry probes, respectively. Some of the homonuclear complexes could be crystallised and were characterised by using X‐ray diffraction studies. The complexes adopt a triple‐stranded helical structure with a central templating cation encapsulated in their interior. An unusual orientation of the double bond of one spacer towards this cation is observed. The homo‐ and heterodinuclear helicates with ytterbium(III), neodymium(III) or erbium(III) of ligands 2 and 4 were of special interest owing to their near‐infrared (NIR) emitting properties, which were investigated depending on the lanthanide and on the encapsulated alkali‐metal cation.     

碳材料表面特性及形貌对阻燃环氧树脂燃烧和热解行为的影响

将制备的4种植物基多孔碳,甘蔗渣炭(SBC)、竹叶炭(BLC)、稻壳炭(RHC)及竹茎炭(BSC),以及购置的椰壳炭(CSC)、果壳炭(NSC)、碳纳米管(CNTs)及可膨胀石墨(EG)分别与聚磷酸铵(APP)复合用于阻燃环氧树脂(EP),研究了碳材料比表面积、表面活性及微观形貌对APP阻燃EP燃烧和热解行为的影响.物理吸附仪、X射线光电子能谱仪(XPS)、扫描电镜研究指出,颗粒状竹茎多孔碳(BSC)的比表面积(2063m2/g)及表面活性基团C—O—、C≡O及COO—的比例显著大于其他碳材料;各种碳材料均以微米级尺度分布于阻燃EP基体.氧指数(LOI)、UL 94垂直燃烧及锥形量热仪研究表明,0.8 wt%BSC或CNTs与3.1 wt%APP协同阻燃EP的LOI分别由EP的24.6%提高到27.3%和27.6%,UL 94均为V-1级,峰值热释放速率分别比EP/APP降低了27%和28%.碳材料的协同阻燃效果主要取决于微观形貌;对于颗粒状多孔碳,其比表面积、O/C比及表面活性基团比例越大,协同阻燃效果越好.热失重分析、共聚焦拉曼光谱及XPS研究证实,碳材料提高了EP/APP复合材料的初始分解温度和残炭量;大的比表面及表面活性,以及管状形貌能够提高环氧树脂复合材料高温残炭量、促进残炭类石墨化转变、改善残炭耐高温氧化性能.     

Zinc(II) and mercury(II) complexes with Schiff bases: syntheses,spectral, and structural characterization

Schiff bases o-vanilidene-1-aminobenzene (HL¹) and o-vanilidene-2-methyl-1-aminobenzene (HL²) lead to the formation of mono- and bis-[(Cl)Zn(L¹)] (1), [(Cl)Zn(L²)] (2), [(Cl)Hg(L¹)] (3), [(Cl)Hg(L²)] (4), [Zn(L¹)₂] (5), [Zn(L²)₂] (6), [Hg(L¹)₂] (7), and [Hg(L²)₂] (8) complexes by reactions of zinc(II) and mercury(II) chlorides in different mole ratio(s). Complexes 1–8 have been characterized by elemental analyses (Zn, Hg, C, H, Cl, and N), melting point and spectral (IR, ¹H-NMR), PXRD, molar conductivity measurement, and TGA. Conductivity measurements suggest non-electrolytes. Structural compositions have been assigned by mass spectral studies. Four-coordinate geometry may be assigned to these complexes tentatively. Structural study reveals that in 1–4 two metal centers are held together by two bridged (μ₂-Cl) chlorides, whereas 5–8 contain two bidentate Schiff-base ligands around one metal-producing monomers.     

Effect of Functionalized Magnetite Nanoparticles and Diaminoxanthone on the Curing,Thermal Degradation Kinetic and Corrosion Property of Diglycidyl Ether of Bisphenol A-Based Epoxy Resin

To prepare a high-performance epoxy resin with excellent thermal, chemical and corrosion stability, diaminoxanthone（DAX） was used to cure diglycidylether of bisphenol-A（DGEBA）-based epoxy resin and blend of DGEBA with functionalized Fe3O4 nanoparticles. Kinetic parameters of curing and thermal degradation of epoxy resin systems were estimated by differential scanning calorimetry（DSC） and thermogravimetric analysis（TGA）, respectively. The 10% weight loss temperature has been increased from 340 °C to 366 °C and there was an increase in the char yield from 32.6% to 45.3% for the above systems. The corrosion performance of epoxy coated carbon steel was examined by potentiodynamic polarization, along with immersion test in 1.0 mol/L HCl solution. The results showed that epoxy resins cured with DAX had low tendency to corrosion. In addition, the cured epoxy resin containing 10% Fe3O4 had higher anticorrosion activity than bare DGEBA system. The results showed that functionalized Fe3O4 nanoparticles enhanced char formation and improved the thermal stability as well as anticorrosion activity of the resin.     

Synthesis and Properties of Complexes of Lead(II), Cadmium(II), and Zinc(II) with N-Phosphonomethylglycine

Summary.  Sparingly water soluble complexes of lead(II), cadmium(II), and zinc(II) with N-phosphonomethylglycine (glyphosate, NPMG) of the general formulae C₃H₆O₅NPPb, C₃H₆O₅NPCdċ2H₂O, and C₃H₆O₅NPZn were synthesized. The complexes were also precipited from a dilute Roundup solution, and their solubility in water was determined. Thermal, diffractometric, and IR spectrophotometric analyses were carried out. It was found that the metal is bonded to glyphosate through the oxygen atoms of the carboxylic and phosphonate groups; metal-nitrogen binding is absent in the above compounds. Studying the complexing behaviour in solution by UV spectrophotometry pointed out that a complex of the composition Pb(II) : NPMG=1:1 with an absorption band at 232 nm is formed. Its stability constant as determined by Job’s method is logK=5.9±0.1. Using potentiometric techniques, the dissociation constant of N-phosphonomethylglycine and the stability constants of its complexes with cadmium (II) and zinc (II) were determined. Received June 30, 1999/Accepted July 21, 1999.     

Polymeric Zn(II) and Cu(II) complexes with exobidentate bridging l-tyrosine: Synthesis,structural and spectroscopic properties

A novel zinc(II) polymeric complex of the formula {[Zn(tyr)₂(H₂O)]H₂O}_n (1) containing l-tyrosine (tyr) was prepared in the crystalline form and characterized by X-ray diffraction, NIR–Vis–UV electronic and IR–FIR vibrational spectroscopy methods. Additionally, for the [Cu(tyr)₂]_n (2) polymer, the vibrational, electronic, EPR spectroscopic and magnetic properties were studied. l-tyrosine in coordination polymers acts as a N,O-bidendate ligand and presents exobidentate bridging with a μ-carboxyl group. The μ-carboxyl exobidentate bridging coordination mode leads to a one-dimensional chain structure. The ZnN₂O₃O′ chromophore has an elongated pseudo-octahedral geometry (1), whereas the CuN₂O₂O′ (2) chromophore presents a distorted square-pyramidal environment with τ = 0.19 around the Cu²⁺ ion.     

Synthesis and spectral characterization of zinc(II) and cadmium(II) complexes of acetone-N(4)-phenylsemicarbazone: Crystal structures of acetone-N(4)-phenylsemicarbazone and a cadmium(II) complex

Seven Zn(II) and Cd(II) complexes of ON donor acetone-N(4)-phenylsemicarbazone (HL) have been synthesized and physico-chemically characterized by partial elemental analyses, molar conductance measurements, infrared, electronic and ¹H NMR spectral studies. The semicarbazone binds the metal as a neutral bidentate ligand in all the complexes. The crystal structures of acetone-N(4)-phenylsemicarbazone and [Cd(HL)₂Cl₂] have been determined by X-ray diffraction studies. The coordination geometry around cadmium(II) in the complex [Cd(HL)₂Cl₂] is distorted octahedral.     

Crystal Structure,Spectroscopic and Thermal Behaviour of Bis(saccharinato)tetrakis(pyridine)nickel(II) Dipyridine

The crystal structure of [Ni(sac)₂py₄] · 2 py (sac = saccharinate anion; py = pyridine) has been solved by single crystal X-ray diffractometry. lt crystallises in the orthorhombic space group Pcan with Z = 4. Coordination of the saccharinate anion to the metal centre occurs, in a rather unusual way, through the carbonylic oxygen atom. The IR and Raman spectra of the complex have been analyzed in detail and assigned on the basis of the structural data. The thermal behaviour was investigated by means of TG and DTA methods.     

Spectrophotometric Simultaneous Determination of Zinc(II), Manganese(II) and Iron(II) in Pharmaceutical Preparations Using OSC-PLS

The purpose of this paper is to develop a fast and sensitive spectrophotometric method for the simultaneous determination of zinc(II), manganese(II) and iron(II) in pharmaceutical preparations. The method presented in this work is based on the well-known reaction of these ions with 4-(pyridylazo)resorcinol (PAR)1. The application of quantitative chemometric methods, particularly PLS to multivariate chemical data is becoming more widespread owing to the availability of digitized spectroscop…     

Studies on mononuclear chelates derived from substituted Schiff-base ligands (part 6): synthesis and characterization of a new 3-ethoxysalicyliden- p -aminoacetophenoneoxime and its complexes with cobalt(II), nickel(II), copper(II) and zinc(II)

Schiff-base complexes of cobalt(II), nickel(II), copper(II) and, zinc(II) with 3-ethoxysalicyliden-p-aminoacetophenoneoxime (HL) were prepared and characterized on the basis of elemental analyses, IR, ¹H- and ¹³C-NMR, electronic spectra, magnetic susceptibility measurements, molar conductivity and thermogravimetric analyses (TGA). A tetrahedral geometry has been assigned to the complexes.     

3-(Aryl)-2-sulfanylpropenoates of mercury(II) and phenylmercury(II)

Compounds [HQ]₂[Hg(L)₂] and [HQ][PhHg(L)] [where HQ = diisopropylammonium cation; L = pspa, fspa, tspa, where p = 3-(phenyl), f = 3-(2-furyl), t = 3-(2-thienyl), and spa = 2-sulfanylpropenoato] have been prepared by the reaction of mercury(II) acetate or phenylmercury(II) acetate with the corresponding acid in the presence of diisopropylamine in ethanol. The compounds have been characterized by elemental analysis, FAB mass spectrometry and IR and NMR (¹H, ¹³C) spectroscopy. The crystal structures of the [HQ]₂[Hg(L)₂] compounds show the presence of diisopropylammonium cations and [Hg(L)₂]²⁻ anions. In each anion the Hg atom is in an HgO₂S₂ environment and this can be described as nido-tbp. The crystal structures of the [HQ][PhHg(L)] compounds show the presence of diisopropylammonium cations and [PhHg(L)]⁻ anions in which the Hg atom adopts an HgCOS distorted T-environment. The NMR data suggest that the coordination mode of the ligand L²⁻ determined by X-ray diffractometry in the solid remains in solution.