3-乙基-2-乙酰吡嗪缩4-苯基氨基脲Ag(Ⅰ)配合物的合成、结构和DNA结合性质

合成并通过单晶衍射、元素分析及红外光谱表征了配合物[Ag₂（HL）（NO₃）₂]_n（1）的结构（HL为3-乙基-2-乙酰吡嗪缩4-苯基氨基脲）。单晶衍射结果表明,配合物1中,HL作为中性四齿配体连接2个Ag（Ⅰ）中心,其中一个Ag（Ⅰ）中心与HL配体中的ON₂供体（羰基O,亚胺N和吡嗪N1原子）和2个单齿硝酸根配位,构成扭曲的四方锥配位构型;而另一个Ag（Ⅰ）离子与1个单齿硝酸根,1个双齿硝酸根和HL配体中的吡嗪N4原子配位,形成扭曲平面正方形配位构型。另外,相邻的Ag（Ⅰ）离子通过桥联的硝酸根离子相互连接形成二维层状结构。此外,配合物1与DNA的相互作用强于配体。     

3-乙基-2-乙酰吡嗪缩4-苯基氨基脲Ag(Ⅰ)配合物的合成、结构和DNA结合性质（英文）

合成并通过单晶衍射、元素分析及红外光谱表征了配合物[Ag_2(HL)(NO_3)_2]_n(1)的结构(HL为3-乙基-2-乙酰吡嗪缩4-苯基氨基脲)。单晶衍射结果表明,配合物1中,HL作为中性四齿配体连接2个Ag(Ⅰ)中心,其中一个Ag(Ⅰ)中心与HL配体中的ON_2供体(羰基O,亚胺N和吡嗪N1原子)和2个单齿硝酸根配位,构成扭曲的四方锥配位构型;而另一个Ag(Ⅰ)离子与1个单齿硝酸根,1个双齿硝酸根和HL配体中的吡嗪N_4原子配位,形成扭曲平面正方形配位构型。另外,相邻的Ag(Ⅰ)离子通过桥联的硝酸根离子相互连接形成二维层状结构;此外,配合物1与DNA的相互作用强于配体。     

3-乙基-2-乙酰吡嗪缩4-苯基氨基脲铜/锌配合物的晶体结构及荧光性质

合成了配合物[Cu（HL）（H₂O）（NO₃）]NO₃（1）和[Zn（HL）Cl₂]（2）（HL为3-乙基-2-乙酰吡嗪缩4-苯基氨基脲）,并通过单晶X射线衍射、元素分析及红外光谱表征了结构。单晶衍射结果表明,配合物1中,中心Cu（Ⅱ）离子与1个中性三齿缩氨基脲配体,1个水分子和1个硝酸根配位,配位构型为扭曲的四方锥。配合物2中Zn（Ⅱ）离子周围的配位原子为N₂OCl₂,其配位构型与配合物1中Cu（Ⅱ）离子的相同。甲醇溶液中,配合物2的荧光发射峰与配体HL相似。而配合物1由于配体和金属离子之间的能量转移,最大荧光发射峰略有红移。     

3-乙基-2-乙酰吡嗪缩4-苯基氨基脲铜/锌配合物的晶体结构及荧光性质

合成了配合物[Cu（HL）（H₂O）（NO₃）]NO₃（1）和[Zn（HL）Cl₂]（2）（HL为3-乙基-2-乙酰吡嗪缩4-苯基氨基脲）,并通过单晶X射线衍射、元素分析及红外光谱表征了结构。单晶衍射结果表明,配合物1中,中心Cu(Ⅱ)离子与1个中性三齿缩氨基脲配体,1个水分子和1个硝酸根配位,配位构型为扭曲的四方锥。配合物2中Zn(Ⅱ)离子周围的配位原子为N₂OCl₂,其配位构型与配合物1中Cu(Ⅱ)离子的相同。甲醇溶液中,配合物2的荧光发射峰与配体HL相似。而配合物1由于配体和金属离子之间的能量转移,最大荧光发射峰略有红移。     

含吡嗪的缩氨基脲配体Ni（Ⅱ）/Cd（Ⅱ）配合物的晶体结构及与DNA的相互作用

合成配合物[NiL₂]·CH₃OH·0.5H₂O（1）和[Cd（HL）Cl₂]（2）（HL=3-甲基2-乙酰吡嗪缩4-苯基氨基脲）并通过单晶衍射、元素分析及红外光谱表征其结构。单晶衍射结果表明,配合物1中,Ni（Ⅱ）离子与2个拥有N₂O电子供体的阴离子配体L-配位,配位构型为扭曲的八面体。而配合物2中,Cd（Ⅱ）离子与1个中性三齿配体HL和2个氯离子配位,拥有扭曲的四方锥配位构型。荧光光谱结果表明,配合物与DNA的相互作用强于配体。     

基于3-乙基-2-乙酰吡嗪缩肼基甲酸甲酯的铜和锌配合物的晶体结构及荧光性质

合成并通过单晶X射线衍射、元素分析及红外光谱表征了配合物[Cu（HL）Cl₂]·H₂O（1）和[ZnL₂]（2）的结构（HL为3-乙基-2-乙酰吡嗪缩肼基甲酸甲酯）。单晶衍射结果表明,在配合物1中,Cu（Ⅱ）离子拥有四方锥配位构型,与一个中性配体HL和2个氯离子配位。配合物2中,Zn（Ⅱ）离子与来自2个阴离子配体L^-的N₂O电子供体配位,配位构型为扭曲的八面体。此外还研究了配合物1和2的固体荧光性质。     

吡嗪缩氨基硫脲Ni（Ⅱ）/Co（Ⅲ）配合物的合成、结构和DNA结合性质

合成并通过单晶衍射、元素分析及红外光谱表征了配合物[Ni（L）（OAc）]（1）和[Co（L）₂]Cl·4CH₃OH（2）的结构（HL为2-乙酰-3-甲基吡嗪-N-（4-氟苯基）缩氨基硫脲）。单晶衍射结果表明,配合物1中,Ni（Ⅱ）离子中心与缩氨基硫脲配体中的NNS供体和1个单齿醋酸根配位,形成扭曲的平面四边形配位构型;在配合物2中,Co（Ⅲ）离子中心与2个三齿缩氨基硫脲配体配位,拥有扭曲的八面体配位构型。此外,荧光光谱表明配合物1和2与DNA的相互作用强于配体。     

吡嗪缩氨基硫脲Ni(Ⅱ)/Co(Ⅲ)配合物的合成、结构和DNA结合性质

合成并通过单晶衍射、元素分析及红外光谱表征了配合物[Ni（L）（OAc）]（1）和[Co（L）₂]Cl·4CH₃OH（2）的结构（HL为2-乙酰-3-甲基吡嗪-N-（4-氟苯基）缩氨基硫脲）。单晶衍射结果表明,配合物1中,Ni（Ⅱ）离子中心与缩氨基硫脲配体中的NNS供体和1个单齿醋酸根配位,形成扭曲的平面四边形配位构型;在配合物2中,Co（Ⅲ）离子中心与2个三齿缩氨基硫脲配体配位,拥有扭曲的八面体配位构型。此外,荧光光谱表明配合物1和2与DNA的相互作用强于配体。     

基于3-乙基-2-乙酰吡嗪缩肼基甲酸甲酯的铜和锌配合物的晶体结构及荧光性质

合成并通过单晶X射线衍射、元素分析及红外光谱表征了配合物[Cu（HL）Cl₂]·H₂O（1）和[ZnL₂]（2）的结构（HL为3-乙基-2-乙酰吡嗪缩肼基甲酸甲酯）。单晶衍射结果表明,在配合物1中,Cu（Ⅱ）离子拥有四方锥配位构型,与一个中性配体HL和2个氯离子配位。配合物2中,Zn（Ⅱ）离子与来自2个阴离子配体L^-的N₂O 电子供体配位,配位构型为扭曲的八面体。此外还研究了配合物1和2的固体荧光性质。     

2-乙酰吡嗪缩肼基甲酸甲酯的镍和镉配合物的晶体结构及荧光性质

合成并通过X射线单晶衍射、元素分析及红外光谱表征了配合物[Ni(L)₂] (1)和[Cd(HL)(CH₃OH)(NO₃)₂] (2)的结构(HL为2-乙酰吡嗪缩肼基甲酸甲酯)。单晶衍射结果表明,配合物1中,Ni(Ⅱ)离子与来自2个阴离子配体L-的N₂O电子供体配位,形成扭曲的八面体配位构型。在配合物2中,Cd(Ⅱ)离子拥有双帽三棱柱配位构型,与1个中性配体HL,2个双齿配位硝酸根和1分子甲醇配位。此外还研究了配合物1和2的荧光及热性质。     

Synthesis of Pd(II) complexes containing the protonated form or molecule of 2-(3,5-dimethylpyrazol-1-yl)-4-methylquinoline (L). The crystal structure of [Pd(HL)Cl<Subscript>3</Subscript>]

The diamagnetic complexes [Pd(HL)Cl₃](I) and PdLCl₂(II), where L is 2-(3,5-dimethylpyrazol-1-yl)-4-methylquinoline, were obtained. According to X-ray diffraction data, the crystal structure of complex I consists of mononuclear acentric molecules. The coordination polygon PdNCl₃ is a distorted square (trapezium) made up of the pyrazole N atom of the monodentate ligand (cation HL⁺) and three Cl atoms. Complex II seems to contain the square polygon PdN₂Cl₂.     

A 2D network silver coordination polymer with the multimodal ligand 2-pyrazyl methyl ketazine

Abstract  

A two-dimensional coordination polymer {Ag(PMK)(OTf)·MeCN} _n (1) based on multi-modal bridging ligand, namely N,N′-bis[1-(pyrazin-2-yl)ethylidene]-hydrazine or 2-pyrazyl methyl ketazine (PMK), and AgOTf salt has been synthesized and characterized by ESI-MS, ¹H-NMR, ATR-IR, and single crystal X-ray diffraction. The PMK shows distinct binding sites, both chelating and monodentate, and bridging modes in 1 where each silver(I) centre is five coordinate, and bound to one bidentate pyrazylketimine and a monodentate pyrazine through the peripheral N atom from another ligand, and also a bridging pyrazine through the peripheral N atom of the adjacent chelating unit from another ligand, and to triflate anion to feature one-dimensional infinite chain. The triflate anions have effectively increased the 1D coordination polymers to a 2D network via H-bonding interactions. These 2D planes are stacked together building up channels (1D tube) in which the acetonitrile solvent molecules reside and form very weak contacts with the triflates and the pyrazylketimine units via C–H···O and C–H···N, respectively. In addition, the fluorescent spectrum of 1 in the solid state exhibits two emission maxima at 496 and 522 nm. The ESI-MS, IR, and ¹H-NMR confirm the structure.     

Syntheses,Crystal Structures and Cytotoxities of Silver (I) Complexes of 2,2′‐Bipyridines and 1,10‐Phenanthroline

The syntheses, characterizations and in vitro cytotoxities of seven soluble silver (I) compounds (1–7) with 2,2′‐bipyridine (bpy), 5,5′‐dimethyl‐2,2′‐bipyridine (dmbpy) and 1, 10‐phenanthroline (phen) are described. Two of the complexes, [Ag(dmbpy)(NO₃)] (1) and [Ag(dmbpy)]ClO₄(2), have been structurally established by single‐crystal X‐ray diffraction, which reveals the silver(I) atom in compound 1 is in a Y‐shape coordination geometry with two N atoms (av. Ag? N = 227.8 pm) from a chelate dmbpy ligand and an O atom (Ag? O=221.8(4) pm) from a monodentate nitrate. The Ag(I) atom in compound 2 is three‐coordinated by three N atoms, two of which are from a chelate dmbpy, and one from an acetonitrile ligand. The seven compounds showed strong cytotoxities in vitro to both normal and carcinoma cells.     

两个含有平行交替链的新型二氰胺配位高聚物: {Mn(dmpz)[N(CN)2]2}2和{Cu(dmpz)[N(CN)2]2}2

Two new dicyanamide coordination polymers, {Mn(dmpz)[N(CN)2]2}2 (1) and {Cu(dmpz)[N(CN)2]2}2 (2)(dmpz=3,5-dimethylpyrazole), were synthesized and characterized by single crystal X-ray diffraction analysis and IR spectroscopy. In 1 and 2 the metal ions have two different coordination modes, where one is coordinated to four dicyanamide anions and two monodentate dmpz molecules to form a slightly distorted octahedral geometry, while the other adopts octahedral geometry, surrounded by four nitrile N atoms and two amide N atoms of the dicyanamide anions. Both complexes contain two alternating chains that are parallel to each other.     

Synthesis,crystal structures and Jack bean urease inhibitory activity of copper(II) complexes with 4-bromo-N′-(2-hydroxy-5-methoxybenzylidene)benzohydrazide

A new hydrazone 4-bromo-N′-(2-hydroxy-5-methoxybenzylidene)benzohydrazide (HL) was prepared and characterized by infrared and UV–vis spectra, as well as single-crystal X-ray diffraction. With the hydrazone as ligand, two new copper(II) complexes were prepared, [Cu₂L₂(NCS)₂]·4H₂O (1) and [CuBrL]·CH₃OH (2). The complexes were characterized by infrared and UV–vis spectra, and single-crystal X-ray diffraction. The Cu in 1 is in a square pyramidal coordination geometry and that in 2 is in a square planar coordination geometry. The two complexes show effective Jack bean urease inhibitory activity, with IC₅₀ values of 23.5 and 2.7 μM, respectively. A molecular docking study of 2 with the urease was performed. The relationship between the structure and urease inhibitory activity indicated that copper complex with square planar coordination is a better model for urease inhibition.     

A novel three‐dimensional AgI coordination polymer based on mixed naphthalene‐1,5‐disulfonate and aminoacetate ligands

The three‐dimensional coordination polymer poly[[bis(μ₃‐2‐aminoacetato)di‐μ‐aqua‐μ₃‐(naphthalene‐1,5‐disulfonato)‐hexasilver(I)] dihydrate], {[Ag₆(C₁₀H₆O₆S₂)(C₂H₄NO₂)₄(H₂O)₂]·2H₂O}_n, based on mixed naphthalene‐1,5‐disulfonate (L1) and 2‐aminoacetate (L2) ligands, contains two Ag^I centres (Ag1 and Ag4) in general positions, and another two (Ag2 and Ag3) on inversion centres. Ag1 is five‐coordinated by three O atoms from one L1 anion, one L2 anion and one water molecule, one N atom from one L2 anion and one Ag^I cation in a distorted trigonal–bipyramidal coordination geometry. Ag2 is surrounded by four O atoms from two L2 anions and two water molecules, and two Ag^I cations in a slightly octahedral coordination geometry. Ag3 is four‐coordinated by two O atoms from two L2 anions and two Ag^I cations in a slightly distorted square geometry, while Ag4 is also four‐coordinated by two O atoms from one L1 and one L2 ligand, one N atom from another L2 anion, and one Ag^I cation, exhibiting a distorted tetrahedral coordination geometry. In the crystal structure, there are two one‐dimensional chains nearly perpendicular to one another (interchain angle = 87.0°). The chains are connected by water molecules to give a two‐dimensional layer, and the layers are further bridged by L1 anions to generate a novel three‐dimensional framework. Moreover, hydrogen‐bonding interactions consolidate the network.     

The Helical Coordination Polymer Ag(Nic)2(NO3)

Single crystals of Ag(Nic)₂(NO₃) were obtained from an aqueous solution of silver nitrate and nicotine as plate‐like colourless crystals. The crystal structure (monoclinic, P2₁, Z = 2, a = 933.3(2), b = 1136.8(2), c = 1024.3(2) pm, β = 94.49(2)°) consists of helical chains in which one nicotine molecule bridges with both the pyridine‐N and the pyrrol‐N coordinating and with a second nicotine molecule terminally coordinating with the pyridine‐N. A monodentate nitrate‐O is completing the coordination sphere of Ag⁺ to a distorted tetrahedron. Ag–N distances (229‐240 pm) attest for a rather strong attraction of the nicotine molecules to Ag(I) and thereby constitute essentially a one‐dimensional, helical coordination polymer according to the formulation Ag(Nic1)_2/2(Nic2)_1/1(NO₃)_1/1.     

Spectral characterization and X-ray structure of two dinuclear complexes constructed by di(2-pyridylcarbaldehyde)-6,6′-dicarboxylic acid hydrazone-2,2′-bipyridine) ligand

Two new bimetallic molecular squares constructed by di(2-pyridylcarbaldehyde)-6,6′-dicarboxylic acid hydrazone-2,2′-bipyridine (H₂L), namely [Cu₂(HL)₂](ClO₄)₂·6H₂O (1) and [Zn₂(HL)₂](ClO₄)₂·2H₂O (2), have been synthesized and characterized by elemental analysis, IR spectra, and X-ray single-crystal diffraction. The architectures of the two bimetallic squares are mainly determined by the cooperation of the metal’s coordination modes and the conformations of H₂L. In 1, the ligand-adopted tridentate plus bidentate bridging modes to give a double helicate, in which two copper(II) ions exhibited two different coordination environments, hex-coordination and penta-coordinated, respectively. While in 2, the ligand-adopted bistridentate bridging modes also to form a double-helicate, in which two zinc(II) ions have the same distorted octahedral geometry. Very interestingly, the overall three-dimensional structures of 1 and 2 contain one-dimensional channels occupied by anions and solvents with H-bonds between square cations and anions. In addition, the solid-state photoluminescent properties of the ligand, complexes 1 and 2 were also studied. The variable-temperature magnetic measurement for the complex 1 shows very weak antiferromagnetic interaction between Cu(II) centers.     

Synthesis and Structural Characterisation of Two Copper(II) Complexes of <Emphasis Type="Italic">N</Emphasis>-(1-acetyl-2-propylidene) (2-pyridylmethyl) amine

Two new complexes [CuBr(C₁₁H₁₃N₂O)] (1) and [Cu(NCO)(C₁₁H₁₃N₂O)] (2) containing the tridentate Schiff base ligand, N-(1-acetyl-2-propylidene)(2-pyridylmethyl) amine which is the 1:1 condensation product of acetylacetone and 2-aminomethylpyridine, have been synthesised and characterised by elemental analysis, IR and electronic spectra, electrochemical study and single crystal X-ray diffraction study. Crystal structures reveal that the copper atom in both the complexes are in square geometry formed by the N₂O donor set of the Schiff base and a bromine atom in 1 and one cyanate ligand in 2. Both bromide and isocyanate ligands act in a terminal monodentate fashion.     

Nickel(II) and cobalt(II) complexes of methyl(2-aminocyclopentene-1-dithiocarboxy)-S-acetate (ACDASAMe)

Nickel(II) and cobalt(II) bis-chelates of methyl(2-aminocyclopentene-1-dithiocarboxy)-S-acetate (ACDASAMe) were synthesized and characterized by spectroscopic methods and in the case of the nickel complex, X-ray single-crystal diffraction. The ligand exhibits the (N, S) coordination mode on interacting with the metal centers. The X-ray structure of the nickel(II) complex reveals a NiN₂S₂ distorted square planar coordination geometry with the ligands showing a cis configuration. There is no interaction between the –CH₂COOMe moieties of the ligand and the metal center, however intermolecular hydrogen bonds through the carbonyl group leads to the building of dimeric associations.