Synthesis,properties, and X-ray crystal structures of two Ag(I) complexes with 2-(pyridin-4-yl)-1H-imidazole-4,5-dicarboxylic acid

Two 1-D and 3-D Ag(I) complexes involving 2-(pyridin-4-yl)-1H-imidazole-4,5-dicarboxylic acid (H₃PIDC) have been characterized by infrared spectrum, elemental analysis, and single-crystal X-ray diffraction. [Ag₂(HPIDC)]_n (1), synthesized under hydrothermal conditions, gave a 3-D framework; [Ag₂(HPIDC)(MBI)]_n (2) (MBI?=?2-methyl-1H-benzo[d]imidazole), with MBI as the second ligand, gave a 1-D zigzag chain and further formed a 3-D supramolecular structure through π···π interactions. The most interesting structural features of these complexes are the presence of C–H···Ag hydrogen bonding interactions and Ag···C weak interactions between the Ag centers and H₃PIDC. Luminescence indicates that 2 has significantly stronger fluorescent emissions than 1 in the solid state at room temperature.     

Synthesis,structure and dielectric properties of a novel Gd coordination polymer based on 2-（ pyridin-4-yl ）- 1H-i midazole-4,B -dicarboxylate

A new Gd coordination polymer based on 2-（pyridin-4-yl）-I H-imidazole-4,5-dicarboxylate （H3PIDC） has been synthesized under hydrothermal conditions, formulated as {[Gd3（HPIDC）3（PIDC）（H2O）4].3H2O}n （1）. The compound crystallizes in the monoclinic system, space group C2/c with a=20.951（7）, b = 9.515（3）, c = 27.483（10） A,β= 106.176（6）°, Z = 4, V= 5262（3） A3, C40 H45 Gd3 N12 O30, Dc = 2.071 g/cm3, Mr=1645.63, λ （MoKa）=0.71073A, μ=3.846mm-1, F（000）=3204, the final R=0.0390 and wR= 0.1332. Complex 1 is a two-dimensional MOF built up from T-shaped 3-connected HPIDC2 , PIDC3 and 4-connected metal nodes. Dielectric constant of complex 1 was measured at different frequencies with temperature variation.     

新的吡啶基硫醚苯甲酸的原位合成及其铜配合物

在氧化铜和溴化铜存在的条件下, 4-[1,2-(2-吡啶基)亚甲硫基]-苯甲酸(L′)经原位消去反应, 形成了一个新的有机配体4-[1,2,2-(2-吡啶基)-(2-吡啶亚甲基)亚甲硫基]-苯甲酸(L), 并与铜形成配位聚合物[Cu₂(L)Br₂]_n(1){L=4-[1,2,2-(2-吡啶基)-(2-吡啶亚甲基)亚甲硫基]-苯甲酸}, 通过红外光谱、元素分析和X射线单晶衍射等手段对其结构进行了表征.     

A series of 2D lanthanide (III) coordination polymers constructed from 2-(pyridin-3-yl)-1H-imidazole-4,5-dicarboxylate

Reactions of 2-(pyridine-3-yl)-1H-4,5-imidazoledicarboxylic acid (H₃PyIDC) with a series of Ln(III) ions affords ten coordination polymers, namely, {[Ln(H₂PyIDC)(HPyIDC)(H₂O)₂]·H₂O}_n [Ln=Nd (1), Sm (2), Eu (3) and Gd (4)], {[Ln(HPyIDC)(H₂O)₃]·(H₂PyIDC)·H₂O}_n [Ln=Gd (5), Tb (6), Dy (7), Ho (8) and Er (9)], and {[Y₂(HPyIDC)₂(H₂O)₅]·(bpy)·(NO₃)₂·3H₂O}_n (10) (bpy=4,4′-bipyridine). They exhibit three types of networks: complexes 1-4 are isomorphous coordination networks containing neutral 2D metal-organic layers, while complexes 5-9 are isomorphous, which consist of cationic metal-organic layers and anionic organic layers, and complex 10 is a 2D network built up from 4-connected HPyIDC²⁻ anion and 4-connected Y(III) ions. In addition, thermogravimetric analyses and solid-state luminescent properties of the selected complexes are investigated. They exhibit intense, characteristic emissions in the visible region at room temperature.     

Hydrothermal synthesis,structure, and photoluminescence of four complexes based on 1H-imidazole-4,5-dicarboxylate or 1H-imidazole-2-carboxylate ligands

Four complexes, [Ag₄(bipy)₂(Himdc)₂(H₂O)₂] _n (1), [Ag(H₂imdc)] _n (2), [K(H₃imdc)(H₂imdc)(H₂O)₂] _n (3), and [Cu(Himc)₂] (4) (H₃imdc?=?1H-imidazole-4,5-dicarboxylic acid, H₂imc?=?1H-imidazole-2-carboxylic acid, and bipy?=?4,4′-bipyridine), were hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis and elemental analysis. The obtained complexes exhibit different coordination structures; 1 contains a 2-D supramolecular layer based on two chains arraying uniformly in an ABAB manner. Compound 2 displays sawtooth-shaped 1-D chains extending to 2-D layers via hydrogen bond interactions. Compound 3 possesses a 3-D framework structure based on a 1-D chain via hydrogen bonding interactions. Compound 4 has a 3-D framework structure bearing a pcu-type topology. In addition, the photoluminescence for 1 has been investigated.     

Synthesis and Characterization of Novel 2-(1,2,3-Triazol-4-yl)-4,5-dihydro-1H-pyrazol-1-yl)thiazoles and 2-(4,5-Dihydro-1H-pyrazol-1-yl)-4-(1H-1,2,3-triazol-4-yl)thiazoles

Reactions of 1-(5-methyl)-1H-1,2,3-triazol-4-yl)ethan-1-ones and benzaldehydes in ethanol under basic conditions gave the corresponding chalcones. Reactions of the chalcones combined with thiosemicarbazide in dry ethanol containing sodium hydroxide afforded the corresponding pyrazolin-N-thioamides. Reactions of the synthesized pyrazolin-N-thioamides and several ketones (namely, ethyl 2-chloro-3-oxobutanoate, 2-bromoacetylbenzofuran, and hydrazonoyl chloride) gave the corresponding novel 2-(1,2,3-triazol-4-yl)-4,5-dihydro-1H-pyrazol-1-yl)thiazoles in high yields (77–90%). Additionally, 2-(4,5-dihydro-1H-pyrazol-1-yl)-4-(1H-1,2,3-triazol-4-yl)thiazoles were obtained in high yields (84–87%) from reactions with N-pyrazoline-thioamides and 4-bromoacetyl-1,2,3-triazoles under basic conditions. The structures of six of the newly synthesized heterocycles were confirmed by X-ray crystallography.     

A new 2-D cobalt coordination polymer with the flexible 2-(1H-imidazole-1-yl)acetate: synthesis,structure, and characterization

A new cobalt coordination polymer with linking unit 2-(1H-imidazole-1-yl)acetate (ima), [Co(ima)₂] _n (1), has been synthesized and structurally characterized by elemental analysis, IR spectra, and X-ray single-crystal diffraction. The X-ray analysis indicates that a neutral 2-D coordination polymer with (3,6) topology was obtained, which shows a 3-D supramolecular network through C–H···O weak interactions. Complex 1 displays mild antimicrobial activity against Achromobacter xylosoxidans ATCC 2706, Bacillus subtilis ATCC 6633, and Candida albicans ATCC 90028, respectively. The magnetic and thermal gravimetric properties for 1 have been investigated and discussed.     

Hydrothermal syntheses and structures of transition metal 2-(4,5-diphenyl-1H-imidazol-2-yl)benzoic acid complexes

Two new transition metal complexes, [Zn(Hdiba)₂(H₂O)]?·?H₂O (1) and [Cu(Hdiba)₂] (2) (H₂diba?=?2-(4,5-diphenyl-1H-imidazol-2-yl)benzoic acid), were synthesized and characterized by IR, elemental analysis, and single-crystal X-ray diffraction. Complex 1 exhibits a monomeric structure, while 2 displays a dimeric structure. Both structures extend to 2-D supramolecular networks via hydrogen bonds. Thermal stabilities of 1 and 2 and photophysical properties of 1 are also discussed.     

Self-assembly of 1-D, 2-D,and 3-D transition-metal coordination polymers based on a T-shaped tripodal ligand 4-(4,5-dicarboxy-1H-imidazol-2-yl)pyridine 1-oxide

Three coordination polymers, {[Co(C₁₀H₅N₃O₅)(H₂O)₂]·H₂O}_n (1), {[Mn₃(C₁₀H₅N₃O₅)₂Cl₂(H₂O)₆]·2H₂O}_n (2), and {[Cu₃(C₁₀H₄N₃O₅)₂(H₂O)₃]·4H₂O}_n (3), based on a T-shaped tripodal ligand 4-(4,5-dicarboxy-1H-imidazol-2-yl)pyridine 1-oxide (H₃DCImPyO), were synthesized under hydrothermal conditions. The polymers showed diverse coordination modes, being characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray structure analysis. In 1, the HDCImPyO^2? generated a 1-D chain by adopting a μ₂-kN, O : kN′, O′ coordination mode to bridge two Co(II) ions in two bis-N,O-chelating modes. In 2, the HDCImPyO^2? adopted a μ₃-kN, O : kO′, O′′ : O′′′ coordination mode to bridge two crystallographically independent Mn(II) ions, forming a 2-D hcb network with {6³} topology. In 3, by adopting μ₄-kN, O : kO′, O′′ : kN′′, O′′′ : O′′′′ coordination, DCImPyO^3? bridged three crystallographically independent Cu(II) ions to form a 3-D framework having the stb topology.     

Construction of three metal-organic frameworks based on multifunctional T-shaped tripodal ligands (4,5-dicarboxy-1H-imidazol-2-yl)pyridine-1-oxide

Three metal-organic frameworks, [Eu(C₁₀H₆N₃O₅)₃(H₂O)₂]?·?H₂O (1), [Tb(C₁₀H₆N₃O₅)₃(H₂O)₂]?·?H₂O (2), and [Cd(C₁₀H₆N₃O₅)₂Cl₂] (3) based on T-shaped tripodal ligands 3-(4,5-dicarboxy-1H-imidazol-2-yl)pyridine-1-oxide and 4-(4,5-dicarboxy-1H-imidazol-2-yl)pyridine-1-oxide (H₃DCImPyO), have been synthesized by the hydrothermal method and characterized by elemental analysis, IR, and single-crystal X-ray structure analysis. The diverse coordination modes of H₃DCImPyO ligands have afforded the three compounds. Complexes 1 and 2 are isomers and the Ln (Ln?=?Eu or Tb) atoms have coordination number eight with a distorted square prism geometry. The partly deprotonated H₂DCImPyO^? ligands display three different coordination modes to link Ln (Ln?=?Tb or Eu) into 1-D double chains. In 3, Cd(II) lies on an inversion center and displays a slightly distorted octahedral coordination. All three compounds exhibit strong fluorescent emissions in the solid state at room temperature.     

Ionothermal syntheses and characterization of 2-D coordination polymers with 4-(1H-imidazol-1-yl) benzoic acid

4-(1H-imidazol-1-yl) benzoic acid and its coordination polymers [M(IBA)Cl] _n (M?=?Zn (1) and Co (2)) have been synthesized. Compounds 1 and 2 were obtained under ionothermal conditions and possess a 2-D laminar [M(IBA)] _n layer based on M₂(CO₂)₂ building blocks with coordinated chloride completing tetrahedral coordination of the metal. Compound 1 exhibits two photoluminescence emission peaks at 410 and 510?nm. The low-energy emission can be attributed to ligand-centered transition and the high-energy band can be assigned to ligand-to-metal charge transfer between the aromatic systems of the organic ligands and the 4s orbitals of Zn(II). The role of the ionic liquid in ionothermal synthesis and crystallization of 1 and 2 are briefly discussed.     

合成3-羟基-2-(4-吡啶基)-1H-茚-1-酮的工艺改进

以邻苯二甲酸酐和4-甲基吡啶为起始原料,正十二烷为溶剂,氯化锌为催化剂,于190℃反应24 h合成了抗癌药物瓦他拉尼的关键中间体——3-羟基-2-(4-吡啶基)-1H-茚-1-酮,收率90.6%,其结构经1H NMR,IR和MS确证。     

Hydrothermal synthesis and crystal structures of two novel rare earth coordination polymers based on pyridine-2,6-dicarboxylic acid

Two novel rare earth coordination polymers, [La(pydc)₂(H₂O)][La(pydc)(H₂O)₂]·H₂O (1) and [Sm(pydc)₂(H₂O)][Sm(pydc)(H₂O)₂]·H₂O (2) (pydc=pyridine-2,6-dicarboxylate) were hydrothermally synthesized and characterized by the elemental analyses, IR spectra and TG analyses. Single crystal X-ray diffractions show that 1 and 2 are isostructural compounds. In the compounds of 1 and 2, the 1D lanthanide helical chains are connected each other by lanthanide binuclear dimer as building blocks to form a novel 3D covalent framework.     

Synthesis of 1-(2,4,6-trichlorophenyl)-2-(1,2,4-triazol-4-yl)-diazene-1-oxide

By reaction of 4-amino-1,2,4-triazole with 1-nitroso-2,4,6-trichlorobenzene in the presence of excess dibromoisocyanurate the title compound was obtained.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 362–364, February, 1992.     

Syntheses,crystal structures and properties of two cadmium coordination polymers containing bis (2-methylimidazol-1-yl)methane(2-mBIM) and bis (imidazol-1-yl)methane (BIM) ligands

Coordination polymers, {[Cd(2-mBIM)₃](ClO₄)₂} _n (1) and [Cd(BIM)₂(NO₃)₂] _n (2), have been prepared from the reaction of bis(2-methylimidazol-1-yl)methane(2-mBIM) with Cd(ClO₄)₂ and bis(imidazol-1-yl)methane (BIM) with Cd(NO₃)₂ in ethanol and water, respectively. Their structures were characterized by single crystal X-ray diffraction and IR spectroscopy. Compound 1 crystallizes in the rhombohedral space group R-3c with a = b = 12.3617(5) Å, c = 38.896(3) Å, γ = 120°, V = 5147.5(5) ų, z = 6. The Cd^II occupies a crystallographic inversion center and is coordinated by six N atoms from six distinct 2-mBIM ligands to form a slightly distorted octahedral geometry. Each 2-mBIM is coordinated to two Cd^II cations, linking alternatively four Cd^II cations, resulting in a 32-membered M₄L₄ macrometallacycle. Compound 2 crystallizes in the monoclinic space group C2/m with a = 14.400(3) Å, b = 9.3894(18) Å, c = 8.6926(17) Å, β = 123.499(2)°, V = 980.1(3) ų, z = 2. The Cd coordinates to four nitrogen atoms from four different BIM and two nitrates to form a slightly distorted octahedral geometry. The BIM ligands bridge to form a 1-D infinite double-bridged chain structure with 16-membered M₂L₂ macrometallacyclic structural units.     

Synthesis, Crystal Structure and Fluorescent Properties of 1-（4-（Dimethylamino）benzylidene）- 4-（naphthalen- 1-yl） Thiosemicarbazide

1 INTRODUCTION Recently, for the fluorescent properties, Schiff base has been more and more important and widely studied in density optical memories, nonlinear op- tics (NLO), organic light-emitting diodes (OLED), polymer LED and electrogenerated chemilumines- cence (ECL)[1~5]. Thiosemicarbazones are a kind of Schiff bases with thiourea and good ligands easily chelating with transition metal ions. Although they have been studied extensively for a long time due to their chemical and b…     

1－（取代吡唑－4－基）－1，2，4－三唑的合成及生物活性研究

合成了２３个新的１－（取代吡唑－４－基）１，２，４－三唑化合物，经ＥＡ、ＩＲ、~１ＨＮＭＲ和ＭＳ确定其组成和结构，并对其进行了抑菌及生长调节活性的初步观察。     

Synthesis of 3-(3-Alkyl-5-thioxo-1H-4,5-dihydro-1,2,4-triazol-4-yl)aminocarbonylchromones

A series of 3-(3-alkyl-5-thioxo-1H-4,5-dihydro-1,2,4-triazol-4-yl)aminocarbonylchromones has been prepared by oxidation of 3-formylchromone with Jones' reagent followed by reaction with 3-alkyl-4-amino-4,5-dihydro-1,2,4-triazole-5(1H)-thione in the presence of POCl³. The structures of the compounds were confirmed by IR, LC-MS, and ¹H NMR spectra and elemental analyses.     

Facile one pot multicomponent synthesis of novel 4-(benzofuran-2-yl)-2-(3-(aryl/heteryl)-5-(aryl/heteryl)-4,5-dihydro-1H-pyrazol-1yl)thiazole derivatives

An efficient base catalyzed one pot multicomponent reaction of aryl/hetryl chalcones, thiosemicarbazide and 1-(benzofuran-2-yl)-2-bromoethan-1-one was developed to synthesize the novel 4-(benzofuran-2-yl)-2-(3-(aryl/heteryl)-5-(aryl/heteryl)-4,5-dihydro-1H-pyrazol-1yl)thiazole derivatives.     

基于4-(2,4-二羧基苯氧基)邻苯二甲酸配体的锌配位聚合物的合成、结构及其荧光传感性能

基于H₄dpa和bpy(H₄dpa=4-(2,4-二羧基苯氧基)邻苯二甲酸,bpy=4,4''-联吡啶)为配体,在水热条件下设计、合成了金属锌配位聚合物(Zn-CP)[Zn(H₂dpa)(bpy)_1.5]_n (1),并用元素分析、红外光谱、X射线单晶衍射等对其进行了结构表征。在1中相邻Zn²⁺与H₂dpa^2-离子和bpy配位形成的一维双链结构,相邻的一维双链通过氢键作用扩展形成三维超分子网结构。荧光研究表明:1是一种灵敏度高、选择性好、多响应的荧光传感器,可用于农药和硝基爆炸物的检测。有趣的是,2,4,6-三硝基苯(TNP)和嘧霉胺(Pth)对1的荧光发射显示出明显的猝灭效果,而抑霉唑(Ima)对1有荧光增强效果。此外,通过紫外可见吸收光谱、荧光寿命以及X射线光电子能谱探究了1的荧光传感机理。