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1.
在水-乙醇混合体系中, 以2-羰基丙酸水杨酰腙(C10H10N2O4)、2,2-联吡啶(C10H8N2, 简写bipy)与Eu(NO3)3•4H2O反应, 首次培养出黄色单晶[Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]•0.5bipy•3H2O. 该晶体属三斜晶系, 空间群为P-1, 晶胞参数a=0.93392(16) nm, b=1.3100(2) nm, c=1.3895(2) nm, α=97.205(3)°, β=105.411(2)°, γ=106.364(2)°, V=15.35(2) nm3, Z=2, μ=2.118 mm-1, Dc=1.686 Mg/m3, F(000)=786, R=0.0116, wR=0.0507, GOF=0.995. 晶体测试结果表明, 该单晶结构为铕的9配位配合物, 两个2-羰基丙酸水杨酰腙分别以负一价和负二价酮式和三个水分子同时参与配位; 每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和C=N中的氮与Eu3+配位, 形成两个共边的稳定五元环, 另三个配位原子则分别来自三个水分子中的氧原子, 该配合物在空间呈扭曲的单帽四方反棱柱, 而在不对称单位中还有游离的一个2,2-联吡啶分子和三个水分子, 这些游离分子与配位分子之间存在大量分子内和分子间氢键, 整个分子在空间呈三维网状结构. 发光性能测试表明该配合物具有很好的荧光性质.  相似文献   

2.
武望婷  胡怀明  王尧宇  史启祯 《化学学报》2005,63(22):2032-2036
在水-乙醇混合体系中, 以2-羰基丙酸水杨酰腙(C10H10N2O4)、2,2-联吡啶(C10H8N2, 简写bipy)与Eu(NO3)3•4H2O反应, 首次培养出黄色单晶[Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]•0.5bipy•3H2O. 该晶体属三斜晶系, 空间群为P-1, 晶胞参数a=0.93392(16) nm, b=1.3100(2) nm, c=1.3895(2) nm, α=97.205(3)°, β=105.411(2)°, γ=106.364(2)°, V=15.35(2) nm3, Z=2, μ=2.118 mm-1, Dc=1.686 Mg/m3, F(000)=786, R=0.0116, wR=0.0507, GOF=0.995. 晶体测试结果表明, 该单晶结构为铕的9配位配合物, 两个2-羰基丙酸水杨酰腙分别以负一价和负二价酮式和三个水分子同时参与配位; 每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和C=N中的氮与Eu3+配位, 形成两个共边的稳定五元环, 另三个配位原子则分别来自三个水分子中的氧原子, 该配合物在空间呈扭曲的单帽四方反棱柱, 而在不对称单位中还有游离的一个2,2-联吡啶分子和三个水分子, 这些游离分子与配位分子之间存在大量分子内和分子间氢键, 整个分子在空间呈三维网状结构. 发光性能测试表明该配合物具有很好的荧光性质.  相似文献   

3.
用非等温热重法研究了Eu(III)的化合物[Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]2·phen·4H2O 的热分解及其动力学,并用Kissinger和Ozawa 方法计算了第一分解阶段的活化能.  相似文献   

4.
在pH≈10的乙醇-水溶液中以硫酸铜、酒石酸和邻菲咯啉反应合成了分子式为[Cu2(C4H2O6)(Phen)2(H2O)]·8H2O的配合物单晶。用X-射线单晶衍射测定了晶体结构,并研究了配合物对大肠杆菌、金黄色葡萄球菌、枯草杆菌的抗菌活性。晶体属单斜晶系,空间群P21。标题化合物为双核铜配合物,2个铜原子配位数不同。Cu(1)是五配位的,具有扭曲的四方锥结构,5个配位原子分别是酒石酸的去质子的羟基氧和羧基氧、邻菲咯啉的2个氮原子及1个水分子的氧原子。Cu(2)为四配位的,配位原子分别是酒石酸的去质子的羟基氧和羧基氧和邻菲咯啉的2个氮原子。分子中Cu(1)…Cu(2)间的距离为0.354 8 nm。存在分子内邻菲咯啉-邻菲咯啉的面—面π-π相互作用,面间距为0.381 3 nm。配合物对大肠杆菌、金黄色葡萄球菌、枯草杆菌具有较强的抗菌活性。  相似文献   

5.
本文采用邻菲罗啉和方酸为配体,在水热条件下通过自组装合成了具有二维网状结构的配位聚合物[Cd(C4O4)(C12N2H8)(H2O)]n,并应用X-光衍射技术测定了其单晶结构。结果表明:Cd原子与2个邻菲罗啉氮原子、3个方酸氧和1个水分子配位,生成了六配位扭曲八面体。方酸以少见的μ-1,2,3配位模式桥联3个中心金属离子,并进一步组装成二维网状配位聚合物。对配位聚合物的光学性能及热稳定性做了进一步的研究,实验结果表明:配位聚合物是具有良好热稳定性的强荧光材料,具有潜在的应用前景。  相似文献   

6.
合成了高氯酸镨和咪唑(C3H4N2), DL-α-丙氨酸(C3H7NO2)混配配合物晶体. 经傅立叶变换红外光谱、化学分析和元素分析确定其组成为[Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3. 使用具有恒温环境的溶解-反应量热计, 以2.0 mol•L-1 HCl为量热溶剂, 在T=(298.150±0.001) K时测定出化学反应PrCl3•6H2O(s)+2C3H7NO2(s)+C3H4N2(s)+3NaClO4(s)=[Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3(s)+3NaCl(s)+5H2O(1)的标准摩尔反应焓为ΔrHmө=(39.26±0.11) kJ•mol-1. 根据盖斯定律, 计算出配合物的标准摩尔生成焓为ΔfHmө{[Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3(s), 298.150 K}=(-2424.2±3.3) kJ•mol-1. 采用TG-DTG技术研究了配合物在流动高纯氮气(99.99%)气氛中的非等温热分解动力学, 运用微分法(Achar-Brindley-sharp和Kissinger法)和积分法(Satava-Sestak和Coats-Redfern法)对非等温动力学数据进行分析, 求得分解反应的表观活化能E=108.9 kJ•mol-1, 动力学方程式为dα/dt=2(5.90×108/3)(1-α)[-ln(1-α)]-1exp(-108.9×103/RT).  相似文献   

7.
合成了高氯酸镨和咪唑(C3H4N2), DL-α-丙氨酸(C3H7NO2)混配配合物晶体. 经傅立叶变换红外光谱、化学分析和元素分析确定其组成为[Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3. 使用具有恒温环境的溶解-反应量热计, 以2.0 mol•L-1 HCl为量热溶剂, 在T=(298.150±0.001) K时测定出化学反应PrCl3•6H2O(s)+2C3H7NO2(s)+C3H4N2(s)+3NaClO4(s)=[Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3(s)+3NaCl(s)+5H2O(1)的标准摩尔反应焓为ΔrHmө=(39.26±0.11) kJ•mol-1. 根据盖斯定律, 计算出配合物的标准摩尔生成焓为ΔfHmө{[Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3(s), 298.150 K}=(-2424.2±3.3) kJ•mol-1. 采用TG-DTG技术研究了配合物在流动高纯氮气(99.99%)气氛中的非等温热分解动力学, 运用微分法(Achar-Brindley-sharp和Kissinger法)和积分法(Satava-Sestak和Coats-Redfern法)对非等温动力学数据进行分析, 求得分解反应的表观活化能E=108.9 kJ•mol-1, 动力学方程式为dα/dt=2(5.90×108/3)(1-α)[-ln(1-α)]-1exp(-108.9×103/RT).  相似文献   

8.
合成了2个新的希土冠醚配合物Ln(NO3)3·C26H38N2O4(Ln=La、Ce; C26H38N2O4=1, 7, 10, 16-四氧-4,13-二氮杂-N,N′-二苄基环十八烷)。通过元素分析,红外光谱,拉曼光谱及其 1H核磁共振谱进行表征。用四圆衍射仪测定了La(NO3)3·C26H38N2O4·CH3CN的晶体结构。晶体属三斜晶系,P1空间群,晶胞参数:a=1.2869(4) nm, b=1.5868(6) nm, c=0.9147(2) nm; α=101.89(2)°, β=105.38(2)°, γ=71.96(3)°; Z=2。dcald.=1.58 g·cm-3, μ(Mo)=13.25 cm-1。中心镧离子与冠醚配体中的4个氧原子和2个氮原子配位,3个硝酸根中的6个氧原子也与La3+配位,形成配位数为12的配合物。  相似文献   

9.
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。  相似文献   

10.
杜桂香  郭惠  焦华  刘晶晶  李珺  张逢星  王大奇 《化学学报》2007,65(24):2863-2867
采用“一锅煮”方法, 在金属Ni(II)离子作用下, 以2-乙酰吡啶和1,2-丙二胺物质的量比为2∶1进行反应, 得到了一种新的闭环单Schiff碱N4四齿配体的配合物[C17H20N4Ni(H2O)Cl]2Cl2•(CH3OH). 配合物的晶体结构测定表明, 其配位单元为N桥连的双核配合物, 配位单元间再通过氢键连接成一维链状结构.  相似文献   

11.
杨锐  何水样  武望婷  陈凤英  胡荣祖 《中国化学》2006,24(12):1731-1736
Europium(Ⅲ) compound with 2-oxopropionic acid salicyloyl hydrazone (C_(10)H_(10)N_2O_4,H_3L) and 1,10-phenan-throline (C_(12)H_8N_2,phen) has been prepared.A yellow prismatic crystal of the compound was obtained,and themolecule crystallized in the triclinic space group P-1.There are two 9-coordinated complex molecules in everystructure unit,where every Eu atom is coordinated by three water molecules and two tridentate C_(10)H_(10)N_2O_4 ligands,forming two stable pentacycles.The coordination polyhedron around Eu~(3+) was described as a single cap squareantiprism.In the crystal cell,there are one free 1,10-phenanthroline and four water molecules.The thermaldecomposition of the compound and its kinetics were studied by non-isothermal thermogravimetry.The Kissinger'smethod and Ozawa's method were used to calculate the activation energy value of the first-step decomposition.Thestages of the decompositions were identified by TG-DTG-DSC curve.The non-isothermal kinetic data were ana-lyzed by means of integral and differential methods.The possible reaction mechanism and the kinetic equationswere investigated by comparing the kinetic parameters.  相似文献   

12.
The binuclear praseodymium(III) complex with N‐(1‐carboxyethylidene)‐salicylhydrazide (C10H10N2O4, H2L) was prepared in H2O‐C2H5OH mixed solution, and the crystal structure of [Pr2L2(HL)2(H2O)4]·3H2O·C6H6 was determined by X‐ray single crystal diffraction. The crystal complex crystallizes in the triclinic system with space group P‐1, and in the structure each Pr atom is 9‐coordinated by carboxyl O and acyl O and azomethine N atoms of two tridentate ligands to form two stable five‐membered rings sharing one side in keto‐mode and two water molecules. The coordination polyhedron around Pr3+ was described as a monocapped square antiprism geometry. In an individual molecule, four tridentate ligands were coordinated by two negative univalent (HL) and two bivalent forms (L) respectively. Two negative univalent ligands were coordinated via μ2‐bridging mode.  相似文献   

13.
In polymeric {[Eu(pzdc)(NO3)(phen)(H2O)]·H2O}n [pzdc is 2,3‐pyrazine­di­carboxyl­ate (C6H2O4) and phen is 1,10‐phenanthroline (C12H8N2)], each europium(III) ion is coordinated by seven O atoms (from three pzdc anions, a nitrate anion and a water mol­ecule) and the two N atoms of the phen ligand, resulting in a nine‐coordinated europium(III) center with a distorted monocapped square‐antiprismatic coordination polyhedron. Four pzdc anions bridge four europium(III) ions, forming a parallelogram unit, the four vertices of which are occupied by the four pzdc anions. Moreover, each parallelogram unit links six other adjacent parallelogram units, forming a two‐dimensional network with disordered lattice water mol­ecules.  相似文献   

14.
Reactions of a freshly prepared Zn(OH)2‐2x(CO3)x · yH2O precipitate, phenanthroline with azelaic and sebacic acid in CH3OH/H2O afforded [Zn(phen)(C9H15O4)2] ( 1 ) and [Zn2(phen)2(H2O)2(C10H16O4)2] · 3H2O ( 2 ), respectively. They were structurally characterized by X‐ray diffraction methods. Compound 1 consists of complex molecules [Zn(phen)(C9H15O4)2] in which the Zn atoms are tetrahedrally coordinated by two N atoms of one phen ligand and two O atoms of different monodentate hydrogen azelaato groups. Intermolecular C(alkyl)‐H···π interactions and the intermolecular C(aryl)‐H···O and O‐H···O hydrogen bonds are responsible for the supramolecular assembly of the [Zn(phen)(C9H15O4)2] complexes. Compound 2 is built up from crystal H2O molecules and the centrosymmetric binuclear [Zn2(phen)2(H2O)2(C10H16O4)2] complex, in which two [Zn(phen)(H2O)]2+ moieties are bridged by two sebacato ligands. Through the intermolecular C(alkyl)‐H···O hydrogen bonds and π‐π stacking interactions, the binuclear complex molecules are assembled into layers, between which the lattice H2O molecules are sandwiched. Crystal data: ( 1 ) C2/c (no. 15), a = 13.887(2), b = 9.790(2), c = 22.887(3)Å, β = 107.05(1)°, U = 2974.8(8)Å3, Z = 4; ( 2 ) P1¯ (no. 2), a = 8.414(1), b = 10.679(1), c = 14.076(2)Å, α = 106.52(1)°, β = 91.56(1)°, γ = 99.09(1)°, U = 1193.9(2)Å3, Z = 1.  相似文献   

15.
Syntheses of the sky blue complex compounds [Ni(H2O)3(phen)(C5H6O4)] · H2O ( 1 ) and [Ni(H2O)2(phen)(C5H6O4)] ( 2 ) were carried out by the reactions of 1,10‐phenanthroline monohydrate, glutaric acid, NiSO4 · 6 H2O and Na2CO3 in CH3OH/H2O at pH = 6.9 and 7.5, respectively. The crystal structure of 1 (P 1 (no. 2), a = 14.289 Å, b = 15.182 Å, c = 15.913 Å, α = 67.108°, β = 87.27°, γ = 68.216°, V = 2934.2 Å3, Z = 2) consists of hydrogen bonded [Ni(H2O)3‐ (phen)(C5H6O4)]2 dimers and H2O molecules. The Ni atoms are octahedrally coordinated by two N atoms of one phen ligand, three water O atoms and one carboxyl O atom from one monodentate glutarato ligand (d(Ni–N) = 2.086, 2.090 Å; d(Ni–O) = 2.064–2.079 Å). Through the π‐π stacking interactions and intermolecular hydrogen bonds, the dimers are assembled to form 2 D layers parallel to (0 1 1). The crystal structure of 2 (P21/n (no. 14), a = 7.574 Å, b = 11.938 Å, c = 18.817 Å, β = 98.48°, V = 1682.8 Å3, Z = 4) contains [Ni(H2O)2(phen)(C5H6O4)2/2] supramolecular chains extending along [010]. The Ni atoms are octahedrally coordinated by two N atoms of one phen ligand, two water O atoms and two carboxyl O atoms from different bis‐monodentate glutarato ligands with d(Ni–N) = 2.082, 2.105 Å and d(Ni–O) = 2.059–2.087 Å. The supramolecular chains are assembled into a 3 D network by π‐π stacking interactions and interchain hydrogen bonds. A TG/DTA of 2 shows two endothermic effects at 132 °C and 390 °C corresponding to the complete dehydration and the lost of phen.  相似文献   

16.
Reactions of 1,10‐phenanthroline monohydrate, Na2C4H4O4 · 6 H2O and MnSO4 · H2O in CH3OH/H2O yielded a mixture of [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O ( 1 ) and [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O ( 2 ). The crystal structure of 1 (P1 (no. 2), a = 8.257(1) Å, b = 8.395(1) Å, c = 12.879(2) Å, α = 95.33(1)°, β = 104.56(1)°, γ = 106.76(1)°, V = 814.1(2) Å3, Z = 1) consists of the dinuclear [Mn2(H2O)4(phen)2(C4H4O4)2] molecules and hydrogen bonded H2O molecules. The centrosymmetric dinuclear molecules, in which the Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms from two H2O molecules and two bis‐monodentate succinato ligands, are assembled via π‐π stacking interactions into 2 D supramolecular layers parallel to (101) (d(Mn–O) = 2.123–2.265 Å, d(Mn–N) = 2.307 Å). The crystal structure of 2 (P1 (no. 2), a = 14.289(2) Å, b = 15.182(2) Å, c = 15.913(2) Å, α = 67.108(7)°, β = 87.27(1)°, γ = 68.216(8)°, V = 2934.2(7) Å3, Z = 2) is composed of the [Mn(phen)2(H2O)2]2+ cations, [Mn(phen)2(C4H4O4)] complex molecules, (C4H4O4)2– anions, and H2O molecules. The (C4H4O4)2– anions and H2O molecules form 3 D hydrogen bonded network and the cations and complex molecules in the tunnels along [001] and [011], respectively, are assembled via the π‐π stacking interactions into 1 D supramolecular chains. The Mn atoms are octahedrally coordinated by four N atoms of two bidentate chelating phen ligands and two water O atoms or two carboxyl O atoms (d(Mn–O) = 2.088–2.129 Å, d(Mn–N) = 2.277–2.355 Å). Interestingly, the succinato ligands in the complex molecules assume gauche conformation bidentately to chelate the Mn atoms into seven‐membered rings.  相似文献   

17.
The title mononuclear [Cu(sq)(phen)2]·3H2O complex [sq is squarate (C4O4) and phen is 1,10‐phenanthroline (C12H8N2)] has been synthesized and the structure consists of a neutral mononuclear [Cu(sq)(phen)2] unit and three solvate water mol­ecules. The CuII ion has distorted square‐pyramidal coordination geometry, comprised of one carboxyl­ate O atom from a monodentate squarate ligand and four N atoms from two chelating phen ligands. An extensive three‐dimensional network of OW—H⋯O/OW hydrogen bonds, face‐to‐face π–­π interactions between the 1,10‐phenanthroline aromatic rings and a weak π–ring interaction are responsible for crystal stabilization.  相似文献   

18.
A Tri‐µ‐O‐S‐O coordinative manganese dimer: [Mn2(SO4)2(phen)4]·CH3OH (phen1,10‐phenanthroline) ( 1 ) was yielded by the reaction of 1,10‐phenanthroline and MnSO4·H2O in a mixed solvent of methanol and acetonitrile under room temperature and was structurally characterized. Single crystal analysis shows that complex 1 has polymeric structure based on binuclear Mn(II) units bridged by O‐S‐O groups of two SO42− anion. The UV spectrum of the complex clarifies that each metal‐organic building unit parallels with each other through the Π‐Π interactions of face‐to‐face separations of two 1,10‐phen planes among the complex, forming a layered structure. And the electronic paramagnetic resonance (EPR) signal clearly indicates that those manganese atoms in complex 1 are in +2 oxidation states.  相似文献   

19.
本文用常温方法合成了钯配合物,化学式[Pd(phen)(L-asp)]•3H2O,并用元素分析和红外图谱的方法进行分析,经单晶X射线衍射对其结构表征。以顺铂为参照,研究了该配合物对三种不同癌细胞(人宫颈癌细胞,肝癌细胞,口腔癌细胞)的细胞毒素作用,结果证明该钯配合物对人宫颈癌细胞有较强的抑制作用。通过多种光谱手段同时研究了该配合物与鱼精DNA作用模式,结果说明通过插入方式阻断鱼精DNA的复制。同时,测定配合物与pBR322质粒DNA作用的凝胶电泳。  相似文献   

20.
The title compound [La(phen)2(H2O)2(NO3)2](NO3) · 2(phen)(H2O) with phen = 1,10‐phenanthroline was prepared by the stoichiometric reaction of La(NO3)3 · 6 H2O and 1,10‐phenanthroline monohydrate in a CH3OH–H2O solution. The crystal structure (triclinic, P 1 (no. 2), a = 11.052(2), b = 13.420(2), c = 16.300(2) Å, α = 78.12(1)°, β = 88.77(1)°, γ = 83.03(1)°, Z = 2, R = 0.0488, wR2 = 0.1028) consists of [La(phen)2(H2O)2(NO3)2]2+ complex cations, NO3 anions, phen and H2O molecules. The La atom is 10‐fold coordinated by four N atoms of two bidentate chelating phen ligands and six O atoms of two H2O molecules and two bidentate chelating NO32– ligands with d(La–O) = 2.522–2.640 Å and d(La–N) = 2.689–2.738 Å. The intermolecular π‐π stacking interactions play an essential role in the formation of two different 2 D layers parallel to (001), which are formed by complex cations and uncoordinating phen molecules, respectively. The uncoordinated NO3 anions and H2O molecules are sandwiched between the cationic and phen layers.  相似文献   

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