糠醛缩对苯二胺与Ln(Ⅲ)配合物的合成、表征及热分解动力学

合成了三种新的希夫碱配合物[LnL2(NO3)2(H2O)2](H2O)(C2H5OH), [Ln(Ⅲ) = Nd, Gd, Dy; L=糠醛缩对苯二胺].通过元素分析、IR、 UV和摩尔电导分析等手段, 对合成的配合物进行了表征, 并用非等温热重法研究了钆配合物的热分解反应动力学. 推断出第三步热分解动力学方程为 dα/dt = A*e-E/RT*3 / 2 (1-α)4/3 [1 / (1-α)1/3-1]-1.     

用非等温DSC曲线确定Ln(NCS)_3·4C_6H_5CH_2NH_2的热分解反应机理函数及热分解反应动力学参数

本文利用非等温DSC曲线对十二种镧系元素异硫氰酸盐与苄胺形成的配合物Ln(NCS)_2.4C_6H_5CH_2NH_2(Ln=La、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb)进行了非等温动力学研究,并运用积分法和微分法进行了分析,推断了它们的热分解反应机理函数,当Ln=La、Pr、Nd、Sm、Eu、Gd时,配合物的热分解动力学方程式da/dt=A·e~(-E/RT·3)(1-α)~(2/3);当Ln=Tb、Dy、Ho、Er、Tm、Yb时,则为dα/dt=A·e~(-E/RT·)(1-α),呈现“钆断”现象.此外还得到了该系列配合物的热分解反应动力学补偿效应表达式.     

三水和硝酸N,N,N"'-四[(1'-苄基-2'-苯并咪唑)甲基]-1,2- 环已二胺合Zn(Ⅱ)的晶体结构和非等温热分解反应动力学

本文报道标题Zn(Ⅱ)配合物:[Zn(NBOCTB)](NO~3)~2.3H~2O的制备,晶体结构及热分解动力学,该晶体属三斜晶系,空间群PI,a=1.4146(2),B=1.5407(3),c=1.8518(4)nm;α=62.09(2).β=72.46(2),68.60(1)°. 并对配合物第一和第二步热分解反应进行了非等温动力学研究.运用Achar法与Coats-Redfern 法对非等温动力学数据进行分析,推断第一步脱水过程为成核生长机理,其动力学方程为d α/dt=Ae^-^E^/^R^T.3/2(1-α).[-ln(1-α) ] ^1^/^3; 动力学补偿效应表达式lnA= 0.3739E- 3. 321. 第二步分解过程为二级化学反应, 其动力学方程为:dα/dt=Ae^E^/^r^t(1-α)^2;动力学补偿效应表达式为lnA=0.2100E-3.690.     

三水和硝酸N,N,N"'-四[(1'-苄基-2'-苯并咪唑)甲基]-1,2- 环已二胺合Zn(Ⅱ)的晶体结构和非等温热分解反应动力学

本文报道标题Zn(Ⅱ)配合物:[Zn(NBOCTB)](NO~3)~2.3H~2O的制备,晶体结构及热分解动力学,该晶体属三斜晶系,空间群PI,a=1.4146(2),B=1.5407(3),c=1.8518(4)nm;α=62.09(2).β=72.46(2),68.60(1)°. 并对配合物第一和第二步热分解反应进行了非等温动力学研究.运用Achar法与Coats-Redfern 法对非等温动力学数据进行分析,推断第一步脱水过程为成核生长机理,其动力学方程为d α/dt=Ae^-^E^/^R^T.3/2(1-α).[-ln(1-α) ] ^1^/^3; 动力学补偿效应表达式lnA= 0.3739E- 3. 321. 第二步分解过程为二级化学反应, 其动力学方程为:dα/dt=Ae^E^/^r^t(1-α)^2;动力学补偿效应表达式为lnA=0.2100E-3.690.     

含有羧基配体的蝎型钒氧配合物的合成、结构及其热分解动力学

设计合成了两种新型的以聚吡唑硼酸盐、氨基酸为配体的钒氧配合物VO[phCH2CH(NH2)COO][HB(pz)3](1)和VO(3,5-Me2pz)[HB(3,5-Me2pz)3](CH3COO)(2). 通过元素分析、红外光谱对配合物进行了表征, 并利用单晶X射线衍射技术解析了它们的结构. 非等温热分解动力学研究表明, 配合物1和2的热分解反应都是分两步进行的. 通过计算, 配合物1热分解的第一步反应的可能机理为成核与生长(n=1/4); 第二步反应的可能机理为化学反应. 其非等温动力学方程分别为, dα/dT=(A/β)e-E/RT(1/4)(1-α)[-ln(1-α)]-3 和dα/dT=(A/β)e-E/RT(1-α)2. 分解反应的表观活化能分别是223.52 和331.94 kJ·mol-1; 指前因子ln(A/s-1)分别是49.67 和57.50. 配合物2 热分解的第一步反应的可能机理为化学反应; 第二步反应的可能机理为成核与生长(n=1/2). 其非等温动力学方程分别为, dα/dT=(A/β)e-E/RT(1-α)2, 和dα/dT=(A/β)e-E/RT(1/2)(1-α)[-ln(1-α)]-1. 分解反应的表观活化能分别是300.56 和444.72 kJ·mol-1; 指前因子ln(A/s-1)分别是75.53 和92.50.     

三水合硝酸N,N,N′,N′-四[(1′-苄基-2′-苯并咪唑)甲基]-1,2-环己二胺合Zn(Ⅱ)的晶体结构和非等温热分解反应动力学

本文报道标题Zn(Ⅱ)配合物:[Zn(NBOCTB)](NO_3)_2·3H_2O的制备,晶体结构及热分解动力学.该晶体属三斜晶系,空间群p(?),a=1.4146(2),b=1.5407(3),c=1.8518(4)nm;α=62.09(2),β=72.46(2),γ=68.60(1)°.并对配合物第一和第二步热分解反应进行了非等温动力学研究.运用Achar法与Coats—Redfern法对非等温动力学数据进行分析,推断第一步脱水过程为成核和生长机理,其动力学方程为:dα/dt=Ae~(-E/RT),3/2(1-α)·[-In(1-α)]~(1/3);动力学补偿效应表达式为:InA=0.3739E-3.321.第二步分解过程为二级化学反应,其动力学方程为:dα/dt=Ae~(-E/RT)(1-α)~2;动力学补偿效应表达式为:InA=0.2100E-3.690.     

钐-对甲基苯甲酸与1,10-邻菲罗啉配合物的合成及热分解动力学

合成了配合物Sm₂(p-MBA)₆(phen)₂(p-MBA：对甲基苯甲酸根离子, phen：1,10-邻菲罗啉)，并用元素分析、红外光谱和紫外光谱进行了表征,采用TG-DTG技术研究了Sm₂(p-MBA)₆(phen)₂在静态空气中的热分解过程，运用一种新的热分析动力学数据处理方法并结合非线性等转化率积分法，进行了动力学分析。同时还确定了峰温处的ΔH^≠, ΔG^≠ 和ΔS^≠的值。用等温TG法得到失重10%为寿终指标的寿命方程为lnτ= –24.7825+18070.43/T.     

稀土配合物Sm2(CH3COO)4(NO3)2(phen)2 的合成、 结构及非等温热分解动力学研究

在水-乙醇混合体系中, 将浓硝酸硝化的Sm2O3与1,10-邻菲啰啉反应, 用冰醋酸调节pH≈4, 形成醋酸根桥联的双核钐配合物［Sm2(CH3COO)4(NO3)2(phen)2］(phen=1,10-邻菲啰啉), 用元素分析、红外光谱和核磁共振谱等进行了表征, 并用X射线衍射测定了配合物的晶体结构, 此外, 对配合物进行了非等温热分解动力学研究. 该晶体属于三斜晶系, P1空间 群, 晶胞参数a=0.979 6(3) nm, b=0.981 3(4) nm, c=1.127 3(4) nm, α=106.666(5)°, β=113.034(5)°, γ=102.656(5)°, V=0.885 4(5) nm3, Z=1, μ=3.361 mm-1, Dc=1.915 g/cm3, F(000)=498, R1=0.059 6, wR2=0.144 8. 该配合物是双核分子, 2个Sm(Ⅲ)离子通过4个醋酸根的羧基桥联, 每个中心离子分别与周围5个来自羧基的桥氧原子、 一个硝酸根的两个氧原子和一个邻菲啰啉分子中的两个氮原子配位, 形成九配位扭曲多面体. 非等温热分解动力学研究结果表明， 配合物第一步热分解反应可能为二级反应, 其动力学方程为dα/dT=A/［βe-E/RT(1-α)2］, 分解反应的表观活化能为344.84 kJ/mol, 指前因子lnA=66.52.     

配合物[Ni（H2B（pyrazolyl）2）2]的非等温热分解动力学研究

在甲醇溶液中用Ni(CH3COO)2.4H2O和NaH2B(pz)2常温下合成出了配合物[Ni(H2B(pz)2)2](pz=pyrazolyl),并用元素分析、红外光谱和X射线衍射等对配合物的结构进行了表征,对此配合物进行了非等温热分解动力学研究.采用了微分Achar和积分Coats-Redfern法分别拟合出配合物2个热分解阶段的动力学方程及相应的动力学参数.配合物第一热分解阶段可能的机理为三维扩散,球形对称,其动力学方程为dα/dT=3(A/β)e-E/RT[(1-α)-1/3-1]-1/2.配合物第二热分解阶段可能的机理为相边界反应,圆柱形对称(n=1/2),其动力学方程为dα/dT=2(A/β)e-E/RT(1-α)1/2.2个反应阶段的表观活化能平均值分别为260.87和176.27kJ/mol,lnA的平均值分别为65.65和37.11s-1.     

Dy(Tyr)(Gly)3Cl3·3H2O的热化学和热分解动力学研究

以氯化镝、甘氨酸和L-酪氨酸为原料合成了配合物Dy(Tyr)(Gly)₃Cl₃·3H₂O. 用溶解-反应热量计测得配合物在298. 15K时的标准摩尔生成焓为–(4287. 10±2. 14) kJ / mol. 并用TG-DTG技术对配合物进行了非等温热分解动力学研究, 推断出配合物第二步热分解反应的动力学方程为: dα/dT＝3. 14 ×10²⁰ s^-1/βexp(-209. 37 kJ / mol /RT)(1-α)².     

Hydrothermal Synthesis,Crystal Structure and Electrochemical Properties of Complex [Cd(phen)_3]·(ClO_4)_2·(p-MBA)_2·(H_2O)_2

One new cadmium complex [Cd(phen)3]·(ClO4)2·(p-MBA)2·(H2O)2 has been hydro-thermally synthesized by reacting p-methylbenzoic acid (p-MBA),1,10-phenanthroline (phen) and cadmium perchlorate. It crystallizes in the triclinic system,space group P1,with a=1.2809(3),b= 1.3431(3),c=1.3734(3) nm,α=84.259(4),β=71.603(3),γ=74.424(3)o,V=2.1594(8) nm3,Dc= 1.532 g/cm3,Z=2,F(000)=1008,μ=0.697 mm-1,R=0.0646 and wR=0.1648. The crystal structure shows that the cadmium ion is coordinated with six nitrogen atoms from three 1,10-phenanthroline molecules,forming a distorted octahedral coordination geometry. The result of electrochemical property analysis shows that the electron transfer in the electrode reaction is irreversible.     

Preparation,Crystal Structure and Thermal Decomposition Process of Dysprosium Benzoate Complex with 1,10.Phenanthroline

A dinuclear dysprosium（III） complex with benzoic acid and 1,10-phenanthroline, [Dy（BA）3phen]2 （BA = benzoate, PHEN = 1,10-phenanthroline） （C66H46Dy2NaO12, Mr = 1412.07） was synthesized and characterized by elemental analysis, UV, IR, X-ray diffraction, molar conductance and TG-DTG techniques. It crystallizes in triclinic, space group P1 with a = 10.773（2）, b = 11.933（3）, c = 12.417（5） A, α= 105.226（3）,β= 93.470（3）, γ= 113.475（2）°, V= 1388.0（7）, Z = 1, Dc = 1.689 g/cm3, μ（MoKa） = 2.742 mm-1 and F（000） = 698. R = 0.0210, wR = 0.0538. In the crystal, each Dy（III） ion is eight-coordinated by one bidentate chelating carboxylate group, four bidentate bridging carboxylate groups and one 1,10-phenanthroline molecule. The thermal decomposition process of [Dy（BA）3phen]2 has been determined by thermal analysis.     

Hydrothermal Synthesis and Crystal Structure of Complex Mn2（phen）2（p-MBA）4（H2O）

A novel Mn（Ⅱ） complex Mn2（phen）2（p-MBA）4（H2O） has been hydrothermally synthesized by the reaction of p-methyl benzoic acid （p-MBA） with 1,10-phenanthroline （phen）. Crystal data for this complex： monoclinic, space group C2/c, a= 2.3328（3）, b =1.5549（2）, c = 1.5557（2） nm, β = 121.726（2）°, V= 4.7997（11） nm^3, Mr = 1028.85, Dc = 1.424 g/cm^3, Z = 4, F（000） = 2128, μ（MoKa） = 0.590mm^-1, GOOF = 1.060, R = 0.0333 and wR = 0.0767. In the crystal, each Mn（Ⅱ） ion is coordinated by two nitrogen atoms from one o-phenanthroline molecule, three oxygen atoms from three p-methyl benzoic acids and one oxygen atom from one water molecule, giving a six-coordinate distorted octahedral coordination geometry. Two neighboring Mn（Ⅱ） ions are bridged by two p-methyl benzoic acid groups and one water molecule, and their end positions are respectively coordinated by one 1,10-phenanthroline and one p-methyl benzoic acid molecule, giving a binuclear cage structure, of which the Mn（Ⅱ）…Mn（Ⅱ） distance is 0.3502 nm.     

配合物[Cu(p-MBA)_2(phen)]的合成、晶体结构及量子化学研究

以醋酸铜、对甲氧基苯甲酸(p-MBA)和邻菲咯啉(phen)为原料在甲醇中反应,合成了一个新的单核铜髤配合物Cu(p-MBA)2(phen),用元素分析和IR等方法对化合物的结构进行了表征。X-射线单晶衍射表明,配合物属单斜晶系,空间群P2/c,晶胞参数:a=1.26503(14)nm,b=0.95588(10)nm,c=1.02488(12)nm,β=105.723(2)°,V=1.1929(2)nm3,Z=2,Dc=1.520g·cm-3,R1[I2σ(I)]=0.0356,wR2[I2σ(I)]=0.0786。该化合物的晶体是由孤立的分子所组成,四配位的铜髤呈畸变的四面体结构,配合物通过分子间弱的C-H…O氢键和π-π堆积作用形成了二维网状结构。对其结构进行量子化学从头计算,探讨了配合物的稳定性、分子轨道能量以及一些前沿分子轨道的组成特征。     

Hydrothermal Synthesis and Crystal Structure of Complex Mn2(phen)2(p-MBA)4(H2O)

A novel Mn(Ⅱ)complex Mn2(phen)2(p-MBA)4(H2O)has been hydrothermally synthesized by the reaction of P-methyl benzoic acid(p-MBA)with 1,10-phenanthroline(phen).Crystal data for this complex:monoclinic,space group C2/c,a=2.3328(3),b=1.5549(2),c=1.5557(2)nm,β=121.726(2)°,V=4.7997(11)nm3,Mr=1028.85,Dc=1.424 g/cm3,Z=4,F(000)=2128,μ(MoKa)=0.590mm-1,GOOF=1.060,R=0.0333 and wR=0.0767.In the crystal,each Mn(Ⅱ)ion is coordinated by two nitrogen atoms from one o-phenanthroline molecule.three oxygen atoms from three P-methyl benzoic acids and one oxygen atom from one water molecule,giving a six-coordinate distorted octahedral coordination geometry.Two neighboring Mn(Ⅱ)ions are bridged by two P-methyl benzoic acid groups and one water molecule,and their end positions are respectively coordinated by one 1,10-phenanthroline and one p-methyl benzoic acid molecule,giving a binuclear cage structure,of which the Mn(Ⅱ)…Mn(Ⅱ)distance is 0.3502 nm.     

Synthesis,Spectroscopic, Thermochemical Properties of Lanthanide Complexes with 3,4-Diethoxybenzoic Acid and 1,10-Phenanthroline

Three novel lanthanide complexes [Ln(3,4-DEOBA)₃phen]₂[Ln=Eu(1), Tb(2), Dy(3); 3,4-DEOBA=3,4- diethoxybenzoate; phen=1,10-phenanthroline] were synthesized and characterized by elemental analysis, molar conductance, X-ray diffraction and infrared spectrometry. The luminescence spectra of complexes 1 and 2 show the characteristic emission of Eu³⁺ ion(⁵D₀→⁷F_0-3) and Tb³⁺ ion(⁵D₄→⁷F_6-3). The thermal decomposition mechanism of the title complexes and the analysis of the evolved gases were investigated by thermogravimetry/differential scanning calorimetry-Fourier transform infrared(TG/DSC-FTIR) technology. The results indicate the complexes are thermally stable. In the thermal decomposition of the complexes, phen molecules lost firstly, and then 3,4-DEOBA ligand decomposed into H₂O, CO₂ and other gaseous molecules. Besides, several gaseous organic fragments were also detected. The heat capacities of complexes 1―3 were measured by DSC in a temperature range of 263.15―340.15 K. Based on the fitted polynomial and thermodynamic equations, the smoothed heat capacities and thermodynamic functions of the three complexes were calculated. The study on biological activity showed that the complexes exhibited good antibacterial activity against Candida albicans, Staphylococcus aureus and Escherichia coli.     

在线固相萃取预富集-原子吸收联用测定痕量Fe(Ⅱ)和总铁量

以1,10-二氮菲(1,10-phen)为配合剂,乙醇为洗脱液,在C₁₈柱上将流动注射固相萃取预富集-原子吸收光谱联用测定痕量Fe(Ⅱ)和总铁.Fe(Ⅲ)的含量可通过抗坏血酸还原后用差示法测得.本法灵敏度高,选择性好,能在线分离干扰富集Fe(Ⅱ),采样速度80次/h,富集倍数19倍,检测下限为3μg/L,相对标准偏差1.1%(n=10),可用于测定水样中痕量Fe(Ⅱ)和Fe(Ⅲ),回收率为94%105%.     

基于对羟基苯乙酸及邻菲咯啉的稀土配合物的合成、晶体结构和荧光光谱

在乙醇-水体系中合成了5个对羟基苯乙酸及邻菲咯啉稀土配合物:其中4个配合物[RE(HPAA)3(phen)2].2H2O(RE=Eu(1),Tb(2),Dy(3),Yb(4))具有相同的结构和类似的化学组成;第5个配合物是[Yb(HPAA)2(H2O)2(phen)2](HPAA).(HHPAA).2H2O(5),HHPAA=对羟基苯乙酸,C8H8O3;phen=1,10-邻菲咯啉),其结构和化学组成与前4个配合物不同。并通过元素分析、红外光谱、热重分析和粉末X-射线衍射对产物进行表征,用单晶X-射线衍射方法测定了配合物5的晶体结构。配合物5(C56H53N4O16Yb)属于三斜晶系,空间群P21/c,晶胞参数:a=2.206 52(3)nm,b=1.368 76(2)nm,c=1.754 14(2)nm,β=101.167(1)°,晶胞体积:V=5.19754(12)nm3,晶胞内结构基元数Z=4,分子量Mr=1211.06。测定了铕、铽和镝配合物的荧光光谱,结果表明,在形成配合物后,依然显示铕髥离子、铽髥离子和镝髥离子的特征发射,这表明配体将吸收的能量有效地转移给了中心离子,配体起到了很好的敏化作用。     

Synthesis, Crystal Structure and Thermal Stability of a Saturated Dimeric Ce(Ⅲ)-chelated Complex Based on Benzoate and 1,10-Phenanthroline Ligands

The title complex, [Ce(BA)3phen]2 (BA = benzoate, phen = 1,10-phenanthroline),was prepared by the reaction of Ce(NO3)3·6H2O, benzoic acid and 1,10-phenanthroline. The complex was characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra and TG-DTG techniques. The results show that the crystal is of triclinic, space group P(1) with a =10.912(2), b = 11.962(3), c = 12.474(3)(A), a = 104.889(3), β = 93.523(3), γ = 113.332(3)°,C66H46Ce2N4O12, Mr = 1366.90, V= 1420.2(6) (A)3, Z = 1, Dc = 1.598 g/cm3,μ = 1.652 mm-1, S =1.024 and F(000) = 682. The final R = 0.0391 and wR = 0.0947 for 4878 observed reflections with I ＞ 2σ(1). The structure of the title complex consists of two Ce(C6H5COO)3(C12H8N2) units,forming a binuclear molecule. Each Ce(Ⅲ) is coordinated by two O atoms of one bidentate chelating carboxylate group, five O atoms of two bidentate bridging and two tridentate chelating-bridging carboxylate groups, and two N atoms of one 1,10-phenanthroline molecule to complete a distorted monocapped square antiprism geometry. Its thermogravimetric analysis was determined by TG-DTG techniques.     

Heteroligand complexes of lanthanides with 4-formyl-3-methyl-1-phenylpyrazol-5-one and 1,10-phenanthroline

Complexes of the general formula LnL₃ · Phen (Ln = Nd, Sm, Eu, Gd, Tb, Dy, and Yb; HL = 4-formyl-3-methyl-1-phenylpyrazol-5-one, Phen = 1,10-phenanthroline) were obtained and examined by IR spectroscopy and thermogravimetry. The structure of the complex TbL₃ · Phen was studied by X-ray diffraction. The coordination polyhedron of terbium is a distorted square antiprism made up of six O atoms of three 4-formylpyrazol-5-one anions and two N atoms of the 1,10-phenanthroline molecule. Polycrystalline samples of the complexes studied show emission in the spectral ranges characteristic of Ln(III).