Coordination of cobalt(III), nickel(II), copper(II), palladium(II) and platinum(II) with N-ethyl-N′-(4′-methylthiazol-2′-yl)thiourea (HL)

Coordination complexes of formula [ML₂], [CoL₃], [Pd(HL)Cl₂], [CuLCl(H₂O)] and [CuL₂(H₂O)₂] {L=anion of N-ethyl-N^′-(4^′-methylthiazol-2′-yl)thiourea; M=Pt^II, Pd^II or Ni^II} were prepared and characterized by elemental analyses, magnetic susceptibilities, and by IR, NMR, electronic and mass spectral measurements.     

4′-(Oxodiphenylphosphino)-2,2′:6′,2′′-terpyridine – crystal structure and complexes of cobalt(II) and cobalt(III)

The complex [Co(2)₂]²⁺ (2 = 4^′-(oxodiphenylphosphino)-2,2^′:6^′,2^′′-terpyridine) has been prepared either by the direct reaction of 2 with Co(II) or by careful oxidation of [Co(1)₂]²⁺(1 = 4^′-(diphenylphosphino)-2,2^′:6^′,2^′′-terpyridine). Further oxidation with H₂O₂ leads to [Co(2)₂]³⁺. The ¹H NMR spectra of the paramagnetic and diamagnetic [Co(2)₂]²⁺ and [Co(2)₂]³⁺ are reported. The crystal structure of ligand 1 has been determined; in the solid-state, 1 exhibits extensive intermolecular π–π stacking.     

Oxidative cyclization and coordinate polymerization of N-benzoyl-N′-(2-pyridyl)thiourea with copper(II) chloride

A chloride-bridged one-dimensional Cu(II) coordination polymer is prepared by the treatment of N-benzoyl-N′-(2-pyridyl)thiourea with a large excess of Cu(II)Cl₂ in ethanol solution via oxidative cyclization and coordinate polymerization.     

Syntheses and structures of cadmium(II) and cobalt(II) coordination polymers based on 1,1′-(2,2′-oxybis(ethane-2,1-diyl))bis(1H-imidazole) and carboxylate ligands

Two novel coordination polymers containing Cd(II) and Co(II) metals, connected via 1,1′-(2,2′-oxybis(ethane-2,1-diyl))bis(1H-imidazole) (L) ligand, have been synthesized. Compound [Cd(L)₂(p-BDC)] · 2H₂O (1) (p-BDC = 1,4-benzenedicarboxylate anion) is a three-dimensional interdigitated supramolecular architecture. Compound [Co(L)(BTCA)_0.5] (2) (BTCA = 1,2,3,4-butanetetracarboxylate anion) possesses a unique (3,4)-connected 3D framework with (8³)₂(8⁵ · 10) topology.     

Coordination Behaviors and Supramolecular Interactions of 2-(2′-Pyridyl) Imidazoline: Crystal Structure of Its Two Cu(II) Complexes

Two new copper coordination complexes, [Cu(PI)(OX)(H₂O)]·H₂O (1) and [Cu(PI)(fum)(H₂O)]·H₂O (2) [PI = 2-(2′-pyridyl) imidazoline, OX^2? = dianion of oxalic acid and fum^2? = dianion of fumaric acid], were synthesized by interface diffusion method based on Cu(II) ions, PI ligands and aliphatic dicarboxylic acids. Complex 1 is a mononuclear complex which spreads into a 3D (4,9)-connected supramolecular network via hydrogen bond interactions, while complex 2 features a 1D zigzag chain with two different orientations. These two compounds are characterized by single crystal X-ray diffraction, powder X-ray diffraction, elemental analyses, infrared spectra, and thermogravimetric analyses.     

Syntheses and Characterization of New Nano-porous Soft Copper(II) Metal–organic Framework and Nano-porous Two-dimensional Manganese(II) and Zinc(II) Coordination Polymers with 4,4′-Bipyridine and 2-Sulfobenzoic Acid

Three new Cu(II), Mn(II), and Zn(II) coordination polymers with 4,4′-bipyridine (4,4′-bipy) and 2-sulfobenzoic acid (2-H₂sb) ligands, [M(4,4′-bipy)(2-sb)(H₂O)]_n, have been synthesized and characterized by IR spectroscopy and elemental analyses. The structures were determined by single-crystal X-ray crystallography. The structural studies show that the metal atoms have six-coordinate geometry with a distorted octahedral environment constructed with 4,4′-bipy and 2-sb²⁻ linkers stacked over each other to generate a two-dimension motif. Self-assembly of these compounds in the solid state is likely caused by coordination and hydrogen-bonds. While polymers containing Zn(II) and Mn(II) have analogous structures, the Cu(II)-containing nano-porous soft metal–organic framework presents a different structure.     

Two novel cadmium(II) coordination polymers based on bis-functionalized ligand 4′-(4-carboxyphenyl)-2, 2′:6′, 2″-terpyridine

Two novel cadmium(II) coordination polymers [Cd(cptpy)₂]_n·nH₂O (1) with a 1D double chain structure and [Cd₂(cptpy)₂(ox)]_n·2.5nH₂O (2) with an interesting 3-connected uninodal six-fold interpenetrating ths network (Hcptpy = 4′-(4-carboxyphenyl)-2,2′:6′,2″-terpyridine, H₂ox = oxalic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, single crystal X-ray diffraction and fluorescence spectra.     

Hydrothermal Synthesis of Cd(II), Mn(II) and Ni(II) Coordination Polymers Derived from Benzopenone-2,4′-carboxylate and N-door Ligands

Three new coordination polymers [Cd(L)(4,4′-bipy)_0.5]_n (1), {[Mn(L)(bpp)]·H₂O}_n (2) and [Ni(L)(2,2′-bipy)(H₂O)₂]_n(3) [H₂L = Benzopenone-2,4′-dicarboxylic acid, 4,4′-bipy = 4,4′-bipy ridine, bpp = 1,3-di(4-pyridyl) propane and 2,2′-bipy = 2,2′-bipyridine] have been synthesized and structurally characterized by elemental analysis, IR and X-ray diffraction. Single-crystal X-ray analyses revealed that the H₂L ligand acts as a bridge, exhibiting three coordination modes to link metal ion: bidentate chelating, bis-monodentate, monodentate. Compound 1 has 3-connected metal–organic framework with the (6³) topology notation; Compounds 2 and 3 are one-dimensional chain structures. The luminescent properties for compound 1 was investigated.     

2-(2′-乙酰氧基-5′-溴甲基苯基)-2H-苯并三唑的合成

2-(2′-羟基-5′-甲基苯基)-2H-苯并三唑(UV-P)经过羟基乙酰化、N-溴代丁二酰亚胺(NBS)溴代,合成了具有高反应活性的2-(2′-乙酰氧基-5′-溴甲基苯基)-2H-苯并三唑。为提高目标产物产率和反应效率,分别对溶剂、引发剂、反应温度、反应时间、反应物投料比和反应底物浓度进行了研究。得出较优合成条件为:氮气保护下,四氯化碳为溶剂,偶氮二异丁腈(AIBN)引发,NBS与2-(2′-乙酰氧基-5′-甲基苯基)-2H-苯并三唑摩尔比1∶1,回流反应1h。在上述条件下,2-(2′-乙酰氧基-5′-溴甲基苯基)-2H-苯并三唑产率为60%。产物经过IR、1HNMR、MS分析证明结构正确。     

2-氰基-2-(3′-氯-2′-硝基苯基)乙酸甲酯的合成

本文主要研究了以 2 ,6 -二氯苯胺为原料 ,经重氮化、取代反应和缩合反应制得 2 -氰基 - 2 - (3′ -氯 - 2′ -硝基苯基 )乙酸甲酯的合成方法 ,通过X -射线分析研究了桑德迈尔反应机理 ,确定了各步最佳反应条件     

Cyano-Bridged Heteropolynuclear Ni(II), Cu(II) and Cd(II) Complexes, [M(deten)2Ni(μ-CN)2(CN)2] n

Three new complexes [M(deten)₂Ni(μ-CN)₂(CN)₂] _n (M = Ni, Cu and Cd, deten = N,N-diethylethylenediamine) have been synthesized and characterized by chemical, thermal analysis, FT-IR and Raman spectroscopies. The crystal structure of the Cd complex has been determined by X-ray single crystal diffraction. Structural study reveals that the Ni²⁺ and Cd²⁺ ions are located on inversion centers, and adopt slightly distorted square-planar and octahedral geometries, respectively. In the crystal structure, the intermolecular N–H⋯N hydrogen bonds link the polymeric chains into a two dimensional network. Vibrational spectral data indicate the presence of two ν(C≡N) for complexes can be assigned to the terminal and bridging cyanides. The decomposition reaction take places in the temperature range 30–1000 °C in the static air atmosphere.     

Carbonyl and chloro complexes of ruthenium(II) containing 3,3′-diester-2,2′-bipyridyl ligands

A series of 3,3′-dialkoxycarbonyl-2,2′-bipyridines (alkyl=Me, Et, i-Pr, i-Bu) has been prepared in good yield from 1,10-phenanthroline. The synthesis and characterization of the corresponding trans-(Cl)-Ru(L)(CO)₂Cl₂ and cis-Ru(L)₂Cl₂ complexes are described.     

Synthesis of soluble polyarylenes containing alternating 4,4′-(1,1′-binaphthyl) and 4,4′-(3,3′-diphenyl)biphenyl structural units

Summary The synthesis and Ni(0) catalyzed homocoupling polymerization of 4,4-bis[5-(trifluoromethanesulfonyloxy)-2-biphenylyl]-1, 1-binaphthyl (9) are described. This polymerization reaction produces a soluble polyarylene containing alternating 4,4-(1,1-binaphthyl) and 4,4-(3,3-diphenyl)biphenyl structural units.     

Syntheses and Characterization of Two New M(II)-5,5′-dimethyl-2,2′-bipyridine (M = Cd and Pb) Coordination Polymers and Study of Their Thermal and Electrochemical Properties

Two new cadmium(II) and lead(II)-thiocyanato coordination polymers with 5,5′-dimethyl-2,2′-bipyridine (5,5′-dm-2,2′-bpy) as chelating ligands were synthesized and characterized by elemental analysis, IR and ¹H NMR spectroscopy and by X-ray crystallography. Thermal and electrochemical properties were also studied as well. These complexes have formed formula [Cd(5,5′-dm-2,2′-bpy)(NCS)₂]_n (1) and [Pb(5,5′-dm-2,2′-bpy)(CH₃COO)(NCS)]_n (2). The coordination numbers of Cd^II in 1 and Pb^II in 2 are six (CdN₄S₂) and seven (PbN₃O₃S₂), respectively. In 2, “stereo-chemically active” electron lone pairs and the coordination spheres were hemidirected. Bridging properties of thiocyanato anions in 1 and 2 created one- and two-dimensional coordination polymers, respectively. The supramolecular features in these complexes were guided and controlled by weak directional intermolecular interactions.     

Metal-Ion Type Effect on the Crystal Structure and Optical Properties of 2,2′-bipyridine Complexes of Pb(II) and Cd(II)

To investigate the effect of metal ion type on the crystal structure and optical and thermal behaviors of coordination compounds, two homometal and one heterometal 2,2′-bipyridine complexes of Pb(II) and Cd(II) have been synthesized and characterized by elemental analysis, PXRD, FT-IR and single crystal X-ray diffraction. Crystal structure analysis of heterometal coordination polymer, [Pb₂Cd(2,2′-bipy)₄(NO₃)₆]_n, displays the attendance of a centrosymmetric 1D coordination polymer that crystallizes in the triclinic system with the space group of \({\text{p}}_{1}^{ - }\). Thermal behavior of prepared coordination compounds was examined under air atmosphere by thermogravimetric analysis. The study of optical properties of compounds showed that metal ion type of coordination compounds is influential on their photophysical properties. Moreover, heterometal coordination polymer was doped into a PVK:PBD blend in two different concentrations as a light emitting material in the fabrication of two organic light-emitting diodes.     

Synthesis,structure and properties of a new copper (II) complex, [Cu2(4,4′-bpy)5(H2O)4](ClO4)4(4,4′-bpy)(DMF)2(H2O)2

A new copper (II) complex with formula [Cu₂(4,4′-bpy)₅(H₂O)₄](ClO₄)₄(4,4′-bpy)(DMF)₂(H₂O)₂ has been synthesized by reaction of 4,4′-bpyridine (4,4′-bpy) with Cu(ClO₄)₂. While strong hydrogen bonds play central roles in the formation of the 3D structure, the combined influence of the weak interactions such as C–H?O bonds, anion?π and C–H?π interactions are also evident in the structure. The preliminary investigation on the thermal property of the complex is presented.     

2-(4′-羟基苯基)-苯并三唑的合成

用改进方法,合成了两个苯并三唑类化合物。以氢氧化钠-碳酸钠水溶液为偶合介质;以保险粉为还原剂,标题化合物的合成收率可提高20％以上。     

4- (2′-甲氧基乙基)苯酚的制备

本文以对硝基甲苯和多聚甲醛为原料,经缩合、甲基化、还原、重氮比、水解等反应制备了合成美多心安的重要中间体4－（2′－甲氧基乙基）苯酚,并对该路线的关键步骤－对硝基甲苯与多聚甲醛的缩合反应进行了优化。得出了较合理的条件为：溶剂：DMSO;催化剂：苯酚钾;配料比：2．50 －1．67。该条件下对硝基甲苯的转化率及选择率可达31％和72％。未反应的对硝基甲苯可回收套用。