New Organotin/CuCN/Quinazoline 3D-Supramolecular Coordination Polymers Having Catalytic and Luminescence Activities

The new bimetallic supramolecular coordination polymers (SCP); ³ _∞[Cu(CN)₂·Me₃Sn·qaz], 1 and ³ _∞[Cu₂(CN)₄·(Ph₃Sn)₂·qaz], 2 (qaz?=?quinazoline), are prepared in water/acetonitrile solvent at room temperature. The structure of 1 consists of the anionic Cu(CN)₂ building blocks connected by the Me₃Sn cations to form zigzag chains which are bridged by qaz creating 2D-sheets. The interwoven infinite sheets are arranged in parallel A···A···A fashion developing 3D-network structure via H-bonds, π–π stacking, and Cu–C contacts. The network structure of 2 exhibits two different copper sites forming two Cu(CN)₂ building blocks which are connected by the Ph₃Sn groups constructing elongated corrugated chains. The qaz ligand connects these chains forming 3D-network structure containing the rhombic [Cu₂(μ₃-CN)₂] motif. 1 and 2 are luminescent materials which can be used in applications as molecular sensing systems. Also, the catalytic activity of 1 and 2 was investigated towards the degradation of Metanil Yellow (MY) dye by dilute solution of hydrogen peroxide as oxidant.     

3D-Supramolecular Coordination Polymer Nanoparticles Based on Cd(II) and Mixed Ligands: Single Crystal X-Ray Structure,Luminescence and Photocatalytic Properties

Nanoparticles of 3D-cadmium supramolecular coordination polymer [Cd(INA)₂(4-aba)], SCP1 (INA?=?isonicotinate anion, 4-aba?=?4- amino benzoic acid), had been synthesized using self-assembly method. SCP1 was characterized by single-crystal X-ray diffraction, elemental analysis, FT-IR and UV/Vis spectroscopy and thermal analysis. SCP1 was also examined by PXRD and transition scanning electron microscopy. Photo-luminescent study of SCP1 as solid sample and suspended in different solvents were also performed. Moreover, the photocatalytic activity of SCP1 under UV-light and sun light irradiation were performed showing high photocatalytic activity for degradation of methylene blue dye. Photo degradation process is mainly caused by ?OH radicals. Mechanism of degradation was also discussed.     

基于含铜簇配位聚合物的制备及晶体结构

通过席夫碱配体2-羟基-3-甲氧基-苯甲醛缩烟酰肼(IAH)和碘化亚铜在溶剂热条件下得到新型的铜(I)配位聚合物[(Cu2I2)L]n。通过元素分析、红外光谱和热重分析等方法对该配合物进行了表征,并测定了它的单晶结构。配合物属三斜晶系,空间群P-1,a=7.998 8(8)?,b=12.642 3(12)?,c=17.919 7(17)?,α=89.528(2)°,β=89.528(2)°,γ=73.688 0(10)°,V=1 738.9(3)?~3,Z=2。     

Synthesis,Characterization and Crystal Structure of New Organotin Copper Cyanide Three-Dimensional Supramolecular Coordination Polymer Containing Quinoxaline Molecule

Self assembly of K₃[Cu(CN)₄] with Me₃SnCl and quinoxaline (qox) affords the new organotin ternary adduct _∞³[Cu₂(CN)₃·Me₃Sn·qox], 1, as orange platelet crystals. The supramolecular architecture of 1 consists of [Cu₂(CN)₃]⁻ building blocks connected by the (Me₃Sn)⁺ cations forming infinite corrugated 1D-chains. The chains are bridged by the qox molecules forming 2D-layers containing fused distorted polygons. The layers are interwoven forming 3D-network structure, which are stabilized by close packing effects such as H-bonds as well as Cu···Cu and π–π interactions. IR and mass spectra as well as TGA are investigated.     

A Novel 3D-Supramolecular Coordination Polymer Based on CuCN,Ph<Subscript>3</Subscript>Sn Cation and Quinoxaline

Reaction of Ph₃SnCl and K₃[Cu(CN)₄] with quinoxaline (qox) at room temperature affords the novel 3D-supramolecular coordination polymer (SCP) _∞³[Cu₂(CN)₄·(Ph₃Sn)₂·qox], I, as the first example of the organotin-CuCN SCP containing the Ph₃Sn fragment. The structure of I displays two Cu(CN)₂ building blocks connected by a Ph₃Sn cation and qox ligand creating the rhombic [Cu₂(μ-CN)₂] motif. The structure of I contains three different fused rings, the minicycle [Cu₂(μ-CN)₂], the 18-atomic [Cu₄(Ph₃Sn)₂(CN)₄(qox)₂], and the 24-atomic [C₈N₈Cu₄(Ph₃Sn)₄] rings, which create a non-interpenetrating 3D-network. These rings form a box-like structure with cavities suitable to accommodate bulky phenyl groups. SCP I belongs to the rapidly growing family of supramolecular assemblies containing the quite unusual [Cu₂(μ-CN)₂] motif, the repeated appearance of which raises the question whether cuprophilic interactions therein are the basic cause of the existence of I.     

Two 3D Coordination Polymers with New Topology Based on Mixed Ligands: Synthesis,Structure, and Photoluminescence Properties

Employing tetracarboxylate and imidazole mixed ligands to react with different transition meat salts afford two new 3D coordination polymers, {[Zn₂(BPTC)(BBI)₂]·(H₂O)₃·DMSO}_n (1) and {[Cd₂(BPTC)(BBI)₂]·H₂O}_n (2) (H₄BPTC?=?biphenyl-3,3′,4,4′-tetracarboxylic acid, BBI?=?1,1′-(1,4-butanediyl)bis(imidazole)). Both these two coordination polymers are 4-connected network topologies. Compound 1 features a unprecedented 3-nodal (4,4,4)-connected network topology with the point symbol {6⁴·8²}, and 2 displays a (4,4)-connected binodal network bearing new topology with the point symbol of {7²·8⁴}2{7³·8³}. Additionally, thermal stability and photoluminescence properties of 1 and 2 were investigated.     

3D-Supramolecular Coordination Polymers as Effective Oxidizing Agents Towards 2,4-Dichlorophenol and 2,6-Di-<Emphasis Type="Italic">t</Emphasis>-butylphenol

3D-supramolecular coordination polymers (SCP) of the type [(R₃Sn)₃Fe^III(CN)₆]; R = CH₃ (I), n-Butyl (II) and phenyl (III) contain wide expandable channels capable of encapsulating and in situ oxidizing 2,4-dichlorophenol (DClP) and 2,6-di-t-butylphenol (DBP) to 2-chloro-1,4-benzoquinone (2-ClBQ) and 3,5,3,5-tertra-t-butyl-4,4-diphenoquinone (BDPQ), respectively, to form new host–guest supramolecular coordination polymers (HGSCP) (1–6). The oxidation products are investigated by spectrophotometry and HPLC methods. A kinetic study indicated a first-order reaction with respect to the hosts SCP I–III. The mechanism and rate of oxidation are discussed in relation to the structure of the SCP.     

Assembly and Fluorescence Properties of 3D-Copper(I) Cyanide Coordination Polymers Based on Methylpyrazine and Tetramethylpyrazine in Presence of Me<Subscript>3</Subscript>SnCl

The reactions of K₃[Cu(CN)₄], Me₃SnCl and methylpyrazine (Me-pyz) or tetramethylpyrazine (Me₄-pyz) in water/dioxane system afforded two new coordination polymers (CP); [{Cu(μ-CN)}₂(μ-Me₄-pyz)·dioxane] _n , 1, and [Cu{μ-Mepyz}{μ-CNSn(Me₃)NC–}], 2. X-ray single crystal analysis shows that 1 contains two crystallographically different copper(I) ions which acquire trigonal planar geometry. The structure of 1 contains non-linear (CuCN)_∞ chains that are interconnected by the Me₄-pyz ligands forming 3D-network structure. The structure of 1 has two-fold interpenetrating 3D-networks with dioxane molecules encapsulated in the voids of the structure. The structures of these CP were also investigated by FTIR and mass spectroscopy, thermal analysis and compared with the prototype compounds. Spectroscopic analyses of 2 confirm the presence of all components (Me₃Sn⁺, Cu(CN)₂ ^? and Me-pyz) and support the composition predicted by elemental analysis. 1 and 2 display strong fluorescence in the solid state at room temperature.     

氰化镀铜液中总氰化物的测定

研究了用气提滴定法测定氰化镀铜液中总氰化物的条件和方法。实验结果表明 ,在 p H<2的磷酸介质中 ,氰化氢易于挥发 ,在空气流量为 0 .8L/min时气提 30 min,气提率可达 99.5%以上。与蒸馏法相比 ,气提法简便易行 ,节电 90 %以上 ,方法的准确度和精密度能满足生产要求。     

Synthesis and Crystal Structures of Two New Coordination Polymers Based on Diphenic Acid

Two new metal coordination polymers [Zn(dpa)(bim)] _n and [Ni(dpa)(bpp)] _n , (H₂dpa = 3,4′-Biphenyl-dicarboxylic acid, bim = Benzimidazole and bpp = 1,3-Di (4-pyridyl)-propane) have been synthesized and structurally characterized by elemental analysis, IR and X-ray diffraction. Single-crystal X-ray analyses reveal that the 3,4′-diphenic acids act as bridging ligands, exhibiting three coordination modes to link metal ions: μ ₂–η ¹: η ¹, μ ₁–η ¹: η ⁰ and μ ₁ –η¹: η¹. Compound 1 demonstrates a one-dimensional zigzag chain. There exists intermolecular hydrogen bonding interactions in compound 1 which lead to form supramolecular structure. Compound 2 is a two-dimensional (4,4) net, and further assembled twofold interpenetrating net. Furthermore, compound [Zn(dpa)(bim)] _n shows intense photoluminescence at room temperature.     

氰化镀铜及乙二胺无氰碱性铜镀体系的EIS研究

以乙二胺为络合剂,研究和测量了氰化镀铜体系和乙二胺无氰镀铜体系的电化学交流阻抗(EIS),考察了乙二胺浓度和pH对EIS的影响。研究结果表明,氰化镀铜体系的电荷转移电阻小,铜离子放电速度快,同时存在电化学极化和浓差极化,这可能是氰化镀铜镀层结合力好的原因之一;乙二胺无氰镀铜体系中,当乙二胺浓度为0.45 mol.L-1,pH=9.0时,电荷转移电阻较小,并且EIS图和氰化镀铜体系的相似。     

A New Pyridine–Diphosphine Ligand for Self-Assembly of Coordination Polymers: Structure of a Polymeric Copper(I) Complex

A new pyridine–diphosphine ligand, N-4-pyridyl-2,2-bis(diphenylphosphinomethyl)propionamide, 1, designed to form polymeric coordination compounds with potential for further self-assembly through amide hydrogen bonding is described. The complex with copper(I) iodide is shown to exist as a polymer with bridging ligands 1. Dedicated to Professor Didier Astruc, especially for his pioneering research on organometallic dendrimers.     

Substituent Effects on Metallo-Supramolecular Coordination Polymers

Dimethyl-substituted bis-terpyridines (L1 and L2) are synthesized as novel ditopic ligand through aldol condensation, Michael-type bis-addition and Suzuki-type cross-coupling. Metallo-supramolecular coordination polymers are obtained by complexation of the bis-terpyridines with metal ions [Ru(II), Fe(II), Co(II)] in suitable solvent. The complexation ratio (1:1) of the ligand with the metal ion in the coordination polymer is confirmed by UV–vis titration experiments and Job’s plot analysis. The binding constants (logK) in the complexation are very high (>9) and the results show that steric hindrance by the methyl groups of the ligand can be ignored in the polymer formation. Their optical, photophysical and electrochemical properties are characterized by UV–vis, luminescence measurements and cyclic voltammetry, respectively, and the substituent effects are discussed. Especially, the luminescence of the Ru(II) polymers is quenched by introduction of the methyl group to bis-terpyridine. Molecular weights of the polymers are estimated by SEC-viscometry-RALS method.     

氰化镀铜锡合金工艺改进

采用正交试验研究了氰化镀铜锡合金工艺中各因素水平的与镀液,镀层性能的关系,优选出一种最佳工艺配方。该工艺成本低,槽液稳定,镀层质量好。     

Construction of Three New Coordination Polymers Based on Dicarboxylate and Different Organic N-Donor Ligands

Three new metal coordination polymers, {[Ni₂(L₁)₂(bip)₂]·H₂O} _n (1), [Zn₂(L₂)₂(bih)_0.5] _n (2) and [Cd(L₂)(bih)_0.5] _n (3) [H₂L₁?=?2-(3-carboxyphenoxy)benzoic acid, H₂L₂?=?2-(4-carboxyphenoxy) benzoic acid, bip?=?4,4??-bis(2-imidazol-1-ylmethyl) biphenyl and bih?=?1,6-bis(2-methylimidazol-1-yl) hexane], have been synthesized and structurally characterized by elemental analysis, IR and X-ray diffraction. Compound 1 is a one-dimensional ladder-like chain structure. Compound 2 is a two-dimensional layer structure. In compound 3, the alternate arrangement of the right- and left-handed helical chains through bih ligands interactions, which lead to form a two-dimensional framework. In compound 1, 2 and 3, the L₁ and L₂ ligands act as bridging ligands, exhibiting three coordination modes to link metal ions: bis-monodentate, bidentate chelating and monodentate modes. Moreover, the luminescent properties of compound 2 and 3 were also investigated in this work.