3d过渡金属的2-羰基丙酸(4-吡啶甲酰基)腙配合物的合成, 表征及导电性质研究

本文制备了2-羰基丙酸(4-吡啶甲酸基)腙(H2PPFH)的六种过渡金属配合物和Mn(II)配合物的单晶。通过元素分析, 红外和紫外光谱, 差热和热重分析对各配合物的结构和性质进行了表征。配合物的通式为M(PPFH).n[H2O(II)=Mn, Fe, Co,Ni, Cu, Zn, n=0～2]。并通过X射线单晶衍射仪对Mn(II)配合物的晶体结构进行了测定。分析表明该晶体属单斜晶系。空间群为P21/n, Z=4, a=1.1252, b=0.9828,c=1.3708nm, β=66.03°, R=0.28。通过配合物的导电性能的测试, 发现它们都具有半导电性质。     

3d过渡金属的2-羰基丙酸(4-吡啶甲酰基)腙配合物的合成, 表征及导电性质研究

本文制备了2-羰基丙酸(4-吡啶甲酰基)腙(H_2PPFH)的六种过渡金属配合物和Mn(Ⅱ)配合物的单晶.通过元素分析、红外和紫外光谱、差热和热重分析对各配合物的结构和性质进行了表征.配合物的通式为M(PPFH)·nH_2O[M(Ⅱ)=Mn,Fe,Co,Ni,Cu,Zn,n=0～2].并通过X射线单晶衍射仪对Mn(Ⅱ)配合物的晶体结构进行了测定.分析表明该晶体属单斜晶系.空间群为P21/n,Z=4,a=1.1252,b=0.9828,c=1.3708nm,β=66.03°,R=0.028.通过对配合物的导电性能的测试,发现它们都具有半导体导电性质.     

铜〔Ⅱ)与咪唑及2-羰基丙酸水杨酰腙混配体配合物的合成、晶体结构及热分解研究

以2-碳基丙酸水杨酰腙、咪唑与五水硫酸铜在水中反应，首次制得混配体配合 物Cu(C10H8N2O4）（C3H4N2）（H2O）[C10H8N2O4^2-为2-羰基丙酸水杨酰腙负离子 ；C3H4N2为咪唑]，并在甲醇溶剂中培养出单晶．该单晶为深绿色，属单斜晶系， 空间群为P2（1）/c，晶胞参数a=1.50583(5)nm,b=1.08411(3)nm,c=0.94366(2)nm, α=90°，β=101.5583(11)°,γ=90°,V=1.50927(7)nm^3,Z=4,μ=1.479mm^-1, Dc=1.628Mg/m^3,F(000)=756.00,R=0.0340,ωR=0.0777,GOF=1.025。晶体测试结果 表明，配合物中Cu(Ⅱ)的配位数为5，处于四方锥配位环境，其中配体2—羰基丙酸 水杨酰腙的羧基以单齿配位．腙基上C≡N的N配位以及碳基(C≡0)的0配位，咪唑的 3位N参与了配位，这四个配位原子处于四方锥的锥底，另一个配位原子来自H20中 的0，它处于四方锥的锥顶．在晶胞中，除分子内存在氢键外，分子间也存在氢键 ．根据TG-DTG曲线研究了配合物的热分解过程，利用Kissinger公式计算了配合物 主要分解阶段的表观活化能．     

二水·2-羰基丙酸水杨酰腙合铜(Ⅱ)配合物的晶体结构及生物活性

在水中,以2-羰基丙酸水杨酰腙与硫酸铜反应,制得新配合物Cu(C₁₀H₈N₂O₄)(H₂O)₂(C₁₀H₈N₂O₄^2-为2-羰基丙酸水杨酰腙负离子),并以水为溶剂培养了单晶,测试了晶体结构,该单晶为深绿色,属单斜晶系,空间群为C2/c,晶胞参数a=1.1297(1)nm,b=0.9824(8)nm,c=2.1973(3)nm,β=91.91(8)°,V=2.43749(8)nm³,Z=8,μ=1.817mm^-1,D_c=1.743Mg·m^-3,F(000)=1304,R=0.0264,wR=0.0654,GOF=1.052。其测试结果表明在配合物中Cu²⁺处于五配位的四方锥配位环境,配位原子分别来自1个三齿配体2-羰基丙酸水杨酰腙负二价离子的2个O原子和1个N原子,2个水分子中的O原子,其中1个水分子的O原子处于四方锥的锥顶,锥底的配位原子基本处于同一平面上。对该配合物所作的皿内抑菌试验和盆栽活体实验表明,配合物对小麦条锈病、白菜黑斑病及辣椒疫霉菌等分别有96%、89%、100%的抑制率,且有一定的助长作用。     

铜(Ⅱ)与2-羰基丙酸水杨酰腙配合物的合成、晶体结构和抑菌活性

以2-羰基丙酸水杨酰腙作为配体与五水硫酸铜进行反应,制得配合物Cu(C₁₀H₈N₂O₄)(H₂O)₂(1)和Cu(C₁₀H₈N₂O₄)(CH₃OH)(H₂O)(2)(C₁₀H₈N₂O₄^2-为2-羰基丙酸水杨酰腙负离子),测试了配合物2的单晶结构.该单晶为墨绿色,属三斜晶系,P1空间群.晶胞参数a=0.7538(2)nm,b=1.1431(2)nm,c=0.7500(2)nm,α=93.26(2)^o,β=94.46(2)^o,γ=94.39(2)^o,V=0.6411(2)nm₃,μ=1.731mm^-1,Z=2,D_c=1.792g/cm³,F(000)=342.00,R=0.035,wR=0.048,GOF=1.78.在配合物2内,2-羰基丙酸水杨酰腙负离子中的2个氧原子和1个氮原子、甲醇中的氧原子以及配位水中的氧原子与铜原子配位,形成四方锥结构,其中来自甲醇的配位氧原子位于锥顶;此晶体为外消旋化合物,晶体中存在对映异构体,两者通过氢键连接,形成二聚体,成对出现在晶胞中.根据元素分析、红外和紫外光谱推测配合物1与2的结构相似;抑菌试验结果表明,配合物1对辣椒疫霉菌和烟草赤星菌分别有100%和66.02%的抑制作用.     

铜(Ⅱ)与咪唑及2-羰基丙酸水杨酰腙混配体配合物的合成、晶体结构及热分解研究

以2-羰基丙酸水杨酰腙、咪唑与五水硫酸铜在水中反应,首次制得混配体配合物Cu(C10H8N2O4)(C3H4N2)(H2O)[C10H8N2O42-为2-羰基丙酸水杨酰腙负离子;C3H4N2为咪唑],并在甲醇溶剂中培养出单晶.该单晶为深绿色,属单斜晶系,空间群为P2(1)/c,晶胞参数a=1.50583(5)nm,b=1.08411(3)nm,c=0.94366(2)nm,a=90°,β=101.5583(11).,γ=90°,V=1.50927(7)nm3,Z=4,μ=1.479 mm-1,Dc=1.628 Mg/m3,F(000)=756.00,R=0.0340,ωR=0.0777,GOF=1.025.晶体测试结果表明,配合物中Cu(Ⅱ)的配位数为5,处于四方锥配位环境,其中配体2-羰基丙酸水杨酰腙的羧基以单齿配位,腙基上C=N的N配位以及羰基(C=O)的O配位,咪唑的3位N参与了配位,这四个配位原子处于四方锥的锥底,另一个配位原子来自H2O中的O,它处于四方锥的锥顶.在晶胞中,除分子内存在氢键外,分子间也存在氢键.根据TG-DTG曲线研究了配合物的热分解过程,利用Kissinger公式计算了配合物主要分解阶段的表观活化能.     

2-甲酰基呋喃苯乙酰腙及其Ni(Ⅱ)配合物的晶体结构及热化学性质

以苯乙酸甲酯、水合肼和呋喃甲醛为原料,合成了配体2-甲酰基呋喃苯乙酰腙(H₂L:C₁₃H₁₂N₂O₂),再与六水氯化镍反应,制得配合物Ni(HL)₂ (1),并对配体及配合物进行了元素分析和X射线单晶衍射结构表征,结果表明,配体晶体属单斜晶系,P2₁/c空间群,晶胞参数为:a=1.161 9(3) nm,b=1.359 8(3) nm,c=0.792 16(19) nm,β=109.307(4)°;Ni(Ⅱ)配合物晶体属三斜晶系,P1空间群,晶胞参数为:a=0.455 70(14) nm,b=1.094 7(3) nm,c=1.204 8(4) nm,β=98.302(5)°。利用热重实验研究了H₂L和1的热稳定性,并计算了各自热分解过程的表观活化能(E_a),发现配合物的热稳定性要远高于配体。采用微量热法研究了H₂L及1与小牛胸腺DNA(CT-DNA)的相互作用,实验结果表明,配合物的作用焓值(ΔH)要大于配体的焓值,说明配合物与CT-DNA的作用要比配体与CT-DNA的作用更强。     

2-甲酰基呋喃苯乙酰腙及其Ni(Ⅱ)配合物的晶体结构及热化学性质

以苯乙酸甲酯、水合肼和呋喃甲醛为原料, 合成了配体2-甲酰基呋喃苯乙酰腙(H₂L：C₁₃H₁₂N₂O₂), 再与六水氯化镍反应, 制得配合物Ni(HL)₂ (1), 并对配体及配合物进行了元素分析和X射线单晶衍射结构表征, 结果表明, 配体晶体属单斜晶系, P2₁/c空间群, 晶胞参数为：a=1.161 9(3) nm, b=1.359 8(3) nm, c=0.792 16(19) nm, β=109.307(4)°;Ni(Ⅱ)配合物晶体属三斜晶系, P1 空间群, 晶胞参数为：a=0.455 70(14) nm, b=1.094 7(3) nm, c=1.204 8(4) nm, β=98.302(5)°。利用热重实验研究了H₂L和1的热稳定性, 并计算了各自热分解过程的表观活化能(Ea), 发现配合物的热稳定性要远高于配体。采用微量热法研究了H₂L及1与小牛胸腺DNA(CT-DNA)的相互作用, 实验结果表明, 配合物的作用焓值(ΔH)要大于配体的焓值, 说明配合物与CT-DNA的作用要比配体与CT-DNA的作用更强。     

二水·2-羰基丙酸水杨酰腙合铜配(Ⅱ)合物的晶体结构及生物活性

在水中,以2-羰基丙酸水杨酰腙与硫酸铜反应,制得新配合物Cu(C10H8N2O4)(H2O)2(C10H8N2O42-为2-羰基丙酸水杨酰腙负离子),并以水为溶剂培养了单晶,测试了晶体结构,该单晶为深绿色,属单斜晶系,空间群为C2/c,晶胞参数a=1.1297(1)nm,b=0.9824(8)nm,c=2.1973(3)nm,β=91.91(8)°,V=2.43749(8)nm3,Z=8,μ=1.817mm-1,Dc=1.743Mg·m-3,F(000)=1304,R=0.0264,wR=0.0654,GOF=1.052。其测试结果表明在配合物中Cu2+处于五配位的四方锥配位环境,配位原子分别来自1个三齿配体2-羰基丙酸水杨酰腙负二价离子的2个O原子和1个N原子,2个水分子中的O原子,其中1个水分子的O原子处于四方锥的锥顶,锥底的配位原子基本处于同一平面上。对该配合物所作的皿内抑菌试验和盆栽活体实验表明,配合物对小麦条锈病、白菜黑斑病及辣椒疫霉菌等分别有96%、89%、100%的抑制率,且有一定的助长作用。     

RE(III)与2-羰基丙酸水杨酰腙配合物的合成、表征及热化学

用2-羰基丙酸水杨酰腙与轻稀土硝酸盐反应,合成了7种新的配合物.经元素分析、化学分析及X射线粉末衍射等手段确定了其组成为RE(C10H9N2O4)(C10H8N2O4)·nH2O(RE=La、Ce、Pr、Nd、Sm、Eu、Gd),用红外、紫外、荧光光谱分析对以上配合物的结构进行了表征;用微热量计测定了稀土芳酰腙配合物的溶解焓,发现其溶解焓数据不随稀土原子序数单调变化,而呈转折变化,可认为呈稀土的四分组现象的前两组.     

稀土-对氨基苯甲酸配合物的合成及结构研究

对氨基苯甲酸与稀土离子在水热条件下反应得到组成为[Ln(p-Ab)3(H2O)]n(p-Ab=对氨基苯甲酸根阴离子,Ln=Sm(1)、Gd(2)、Er(3))的配位聚合物,而Gd(Ⅲ)离子与对氨基苯甲酸在常规溶液条件下反应得到组成为{[Gd(p-Ab)3(H2O)2].H2O}2(4)的双核配合物。配合物(1)-(3)晶体属单斜晶系,P2(1)/n空间群;中心离子配位数为8。配合物为二维层状结构。配合物(4)为双核结构,配体氨基未参与配位。其晶体属三斜晶系,Pī空间群。配位多面体为8配位的双帽三角棱柱体。     

Mechanochemical syntheses,crystal structures,and photo-luminescent properties of a new hydrazone and its nickel and cadmium complexes

Abstract

A new hydrazone, ethyl Z-2-(pyridine-2yl-methylene)hydrazinecarboxylate (C₉H₁₁N₃O₂; Hpyec) and its metal complexes bis(ethyl Z-2-(pyridine-2yl-methylene)hydrazinecarboxylate)nickel(II) monohydrate, [Ni(pyec)₂]·H₂O (1) and bis(acetato)(ethyl Z-2-(pyridine-2yl-methylene)hydrazinecarboxylate)cadmium(II), [Cd(Hpyec)(CH₃COO)₂] (2), have been prepared by mechanochemical syntheses and characterized by elemental analysis, UV–vis, IR and NMR spectroscopies, TG-DTA, and solid state emission techniques. The X-ray single crystal structures of both complexes were determined. In 1, the Ni²⁺ ion is coordinated by two N,N,O-tridentate anionic ligands to generate a distorted cis-NiO₂N₄ octahedron. In 2, the cadmium ion is seven-coordinate by one neutral N,N,O-tridentate ligand and two chelating acetate ions to generate a very-distorted CdN₂O₅ pentagonal bipyramid with the Hpyec atoms occupying both axial and one equatorial site. Crystal data: 1, C₁₈H₂₂N₆NiO₅, M_r?=?461.12, monoclinic, P2₁/c, a?=?10.8759(3) Å, b?=?11.7055(4) Å, c?=?16.8424(5) Å, β?=?108.583(1)°, V?=?2032.38(11) ų, Z?=?4, R(F)?=?0.023, wR(F²)?=?0.065; 2, C₁₃H₁₇CdN₃O₆, M_r?=?423.69, monoclinic, Cc, a?=?13.0215(10) Å, b?=?15.8104(11) Å, c?=?7.99(6) Å, β?=?96.692(2)°, V?=?1621.7(2) ų, Z?=?4, R(F)?= 0.017, wR(F²)?=?0.038.     

Studies on the thermal decomposition of rare earth element complexes with 2-naphthoic acid

Journal of Thermal Analysis and Calorimetry - The rare earth element 2-naphthoates were prepared as crystalline solids sparingly soluble in water (10?5?10?6 mol·dm?3),...     

Crystal structures and thermal decomposition mechanism of four lanthanide complexes with halogen-benzoic acid and 1,10-phenanthroline

This paper describes syntheses and structure determination of four lanthanide complexes [Nd(2-Cl-4-FBA) 3 phen] 2 (1, 2-Cl-4-FBA = 2-chloro-4-fluorobenzoate, phen = 1,10-phenanthroline), [Ln(2,5-DClBA) 3 phen] 2 (Ln = Sm(2) and Tb(3), 2,5-DClBA = 2,5-dichlorobenzoate) and [Sm(2-Cl-4,5-DFBA) 3 (phen)(H 2 O)] 2 (4, (2-Cl-4,5-DFBA = 2-chloro-4,5-difluorobenzo- ate). The complexes were characterized by elemental analysis, infrared and ultraviolet spectra, and X-ray single-crystal diffraction. In the molecular structures of 1 4, two Ln 3+ ions are linked by four carboxyl groups, with two of them in a bridging bidentate mode and the other two in a bridging-chelating tridentate mode, forming four binuclear molecules. In addition, each Ln 3+ ion is also chelated to one phen molecule and one carboxyl group in the complexes, except each Sm 3+ ion in 4 which is bonded to one carboxyl group by unidentate mode and one H 2 O molecule. There are two different coordination polyhedrons for each Nd 3+ ion in the two similar molecular structures of 1 and they are a distorted monocapped square antiprismatic and a distorted tricapped triangular prism conformation, respectively. The coordination polyhedron for each Ln 3+ ion in 2 4 is a nine-coordinated distorted mono-capped square antiprismatic conformation. The complex 3 exhibits green luminescence under the radiation of UV light. The thermal decomposition behaviors of the complexes have been discussed by simultaneous TG/DSC-FTIR technique. The 3D surface graphs for the FTIR spectra of the evolved gases were recorded and the gaseous products were identified by the typical IR spectra obtained at different temperatures from the 3D surface graphs. Meanwhile, we discussed the nonisothermal kinetics of 1 4 by the integral isoconversional non-linear (NL-INT) method.     

Weak alkali and alkaline earth metal complexes of low molecular weight ligands in aqueous solution

This work is aimed at reviewing the chemical literature dealing with thermodynamic aspects of the weak complex formation (species with log K values less than about 3) between alkali and alkaline earth metal ions with low molecular weight inorganic and organic ligands in aqueous solution. The following ligands (up to hexavalent anions) were examined in detail: (i) hydroxide, chloride, sulfate, carbonate and phosphate as inorganic, and (ii) carboxylates, amines, amino acids, complexones and nucleotides as organic ligands. The paper also identifies the main reasons responsible for the dispersion of the stability data on ion pairs in the literature. When possible, the trend of stability for the different metal ions interacting with the same ligand will be considered to find predictive interaction relationships. Since the stability of weak alkali and alkaline earth metal complexes are mainly due to electrostatic interaction, simple empirical relationships were obtained between log K and the charge of the anionic ligand. The interest for alkali and alkaline earth cations rises since they are used in study of basic science as components of the supporting electrolyte and are widely diffused in natural fluids. Some examples of application of this science were presented too, to show the role of weak complex formation in the modelling process of natural systems.     

碱土金属钨铬杂多配合物的合成、表征及热稳定性研究

用直接法合成了以Cr为中心原子的碱土金属和W的三元杂多配合物,经ICP和TG曲线确定其化学式为K7[CrA(H2O)W11O39].xH2O(A=Mg2 ,Ca2 ,Sr2 和Ba2 ),采用IR,UV,XRD,XPS和183W NMR等手段对配合物结构进行了表征,确认所合成的配合物为-αKeggin结构.借助TG-DTA详细讨论了配合物的热稳定性,得出合成配合物的热稳定温度为450℃左右.     

Synthesis,characterization and crystal structures of Ni(II), Cd(II) complexes with N -(2-propionic acid)-salicyloyl hydrazone and bipy/phen

The ligand N-(2-propionic acid)-salicyloyl hydrazone(H₃L, 1) and its new transition metal(II) complexes [NiHL(bipy)H₂O] (2), [CdHL(bipy)(H₂O)₂]₂·2H₂O (3) and [NiHL(phen)H₂O]·H₂O (4) (HL is a dianion, bipy?=?2,2′-bipyridine and phen?=?1,10-phenanthroline) were synthesized and characterized on the basis of elemental analyses, IR, ¹H NMR, molar conductivity and thermal analysis. Single crystal X-ray diffraction showed that 1 is in keto form and connected by hydrogen bonds to form a two-dimensional supermolecular compound. Complexes 2 and 4 have the same structure with distorted meridional octahedral geometry with 1 as a tridentate ligand with keto-form coordination by azomethine, carboxyl O and acyl O. In 3, ligand 1 bridges two Cd(II) atoms by μ ₂-O of carboxyl. H-bonding is an important weak interaction for constructing supermolecular frameworks. There are π–π interactions between bipy or phen rings in 3 or 4, respectively.     

Rare earth complexes with 4-methylmorpholine-N-oxide

Complexes of rare earth trifluoroacetates (TFA) with 4-methylmorpholine-N-oxide (MMNO) of composition Ln(TFA)3·3MMNO (Ln=Eu, Dy, Ho, Er, Yb and Y) were synthesized and characterized by elemental analysis data, complexometric titration with EDTA, IR absorption spectra, thermogravimetric analyses and differential scanning calorimetry (DSC) in N₂ atmosphere. Infrared spectroscopy data revealed that the MMNO molecules are bound to the central ion through the oxygen of NO groups. These data suggest that the trifluoracetate groups are also coordinated. Thermogravimetric curves indicate that the decomposition of MMNO begins at approximately 350 K and results in Ln₂O₃ residue at around 1170 K. A theoretical kinetic study was carried out using a QBASIC program with the TG input data for the Dy complex. This revised version was published online in August 2006 with corrections to the Cover Date.     

Two novel alkaline earth coordination polymers constructed from cinnamic acid and 1,10‐phenanthroline: synthesis and structural and thermal properties

In coordination chemistry and crystal engineering, many factors influence the construction of coordination polymers and the final frameworks depend greatly on the organic ligands used. The diverse coordination modes of N‐donor ligands have been employed to assemble metal–organic frameworks. Carboxylic acid ligands can deprotonate completely or partially when bonding to metal ions and can also act as donors or acceptors of hydrogen bonds; they are thus good candidates for the construction of supramolecular architectures. We synthesized under reflux or hydrothermal conditions two new alkaline earth(II) complexes, namely poly[(1,10‐phenanthroline‐κ²N,N′)bis(μ‐3‐phenylprop‐2‐enoato‐κ³O,O′:O)calcium(II)], [Ca(C₁₀H₇O₂)₂(C₁₀H₈N₂)]_n, (1), and poly[(1,10‐phenanthroline‐κ²N,N′)(μ₃‐3‐phenylprop‐2‐enoato‐κ⁴O:O,O′:O′)(μ‐3‐phenylprop‐2‐enoato‐κ³O,O′:O)barium(II)], [Ba(C₁₀H₇O₂)₂(C₁₀H₈N₂)]_n, (2), and characterized them by FT–IR and UV–Vis spectroscopies, thermogravimetric analysis (TGA) and single‐crystal X‐ray diffraction analysis, as well as by powder X‐ray diffraction (PXRD) analysis. Complex (1) features a chain topology of type 2,4 C4, where the Ca atoms are connected by O and N atoms, forming a distorted bicapped trigonal prismatic geometry. Complex (2) displays chains of topology type 2,3,5 C4, where the Ba atom is nine‐coordinated by seven O atoms of bridging/chelating carboxylate groups from two cinnamate ligands and by two N atoms from one phenanthroline ligand, forming a distorted tricapped prismatic arrangement. Weak C—H…O hydrogen bonds and π–π stacking interactions between phenanthroline ligands are responsible to the formation of a supramolecular three‐dimensional network. The thermal decompositions of (1) and (2) in the temperature range 297–1173 K revealed that they both decompose in three steps and transform to the corresponding metal oxide.     

Helical ternary complexes of alkaline earth picrates with open-chain crown ether

Much attention has been paid to the amide-type open-chain crown ethers with versatile mo-lecular structures because of their characteristic physical and chemical properties. These types of ligands have been used successfully as the active materials for ion-selective electrodes and the extractants for metal ions[1—5]. Among these ligands, N,N,N′,N′-tetraphenyl-3,6,9-trioxaun- decanediamide (TTD) shows the high extractabilities for Sr2+, Ba2+ and rare earth ions and the good selectivity to…