羧酸铜与单螺旋吡啶胺配体自组装的两种新型超分子配合物

Two novel supramolecular complexes [Cu（bpapa）（dhbd）]·CHaOH （1） and [Cu（bpapa）（ma）]·ma （2） （bpapa= bis[6-（2-pyridylamino）pyrid-2-yl]amine, dhbd=2,3-dihydroxybutanedioate dianion, ma=a-methacrylate） were rationally designed, synthesized and characterized by single crystal X-ray diffraction, IR, electronic spectroscopy and thermogravimetric analyses. Complex 1 was the first oligo-a-pyfidylamino complex based on hydroxypolycarboxylate and self-assembled into a 3D honeycomb configuration network with open channels and tubes containing 1D ladder-shaped double chains formed by hydrogen bonds and aromatic π-π stacking interactions. Complex 2 constructed a 2D supramolecular network extended by 1D chains from dimeric supramolecular synthon through noncovalent supramolecular interactions. In the two complexes, the chelating monohelical ligand adopted all-anti configuration. Density functional theory calculations were applied to 1 and 2.     

Syntheses, Structures and Luminescent Property of Two Supramolecular Complexes Containing N-P-Acetamidobenzenesulfonyl-glycine Acid Ligand

Making use of N-P-acetamidobenzenesulfonyl-glycine acid （abbreviated as abglyH2）,two transitional metal complexes [Zn（abglyH）（phen）2]ClO4·H2O （1） and Co（abglyH）2（bipy）2（H2O）2 （2） （phen = 1,10-phenanthroline,bipy = 4,4＇-bipyridine） have been synthesized under mild conditions and characterized by IR,elemental analysis and X-ray diffraction analysis. Complex 1 is a monomeric compound which is further assembled by intermolecular hydrogen bonds and π-π interaction into a 2-D supramolecular network. Complex 2 is also a monomeric compound and further connected by intermolecular hydrogen bonds to form a 2-D supramolecular network. Fluorescent analysis shows that complex 1 has an emissive maximum at 364 nm in the solution state at room temperature.     

Syntheses,Structures and Properties of Three Transition Metal Coordination Polymers Based on Semi-rigid 3-Pyridylnicotinamide and S/N-Containing Dicarboxylate Mixed Ligands

Three new coordination complexes, [Co（L）（ADTZ）]·H2O（1）, [Cd（L）（ADTZ）]·H2O（2） and [Zn（L）（ADTZ）]·H2O（3）[L=3-pyridylnicotinamide, H2ADTZ=2,5-（s-acetic acid）dimercapto-1,3,4-thiadiazole], were synthesized under hydrothermal conditions. These complexes were structurally characterized by single-crystal X-ray diffraction analysis and further characterized by infrared spectroscopy（IR）, powder X-ray diffraction （PXRD） and thermogravimetric analysis（TGA）. Complexes 1-3 exhibit the similar 2D double-layer networks based on 1D [M-L], zigzag chains and 1D [M-ADTZ]2n double-chains with different distances between metal ions and with various conformations of ADTZ anions. In complexes 1 and 3, the 2D sheets are extended into a 3D supramolecular frameworks by hydrogen bonding interactions. The subtle effects of the central metal atoms on the structures of the title coordination polymers were discussed. The electrochemical properties of complex 1 and luminescent properties of complexes 2 and 3 were investigated. In addition, complexes 1-3 exhibit photocatalytic activity for dye methylene blue degradation under UV light and show good stability toward photoca- talysis.     

Synthesis,Crystal Structure and Blue Photoluminescence of a Metal-organic Framework Constructed from Triangular [Zn3（μ3-OH）] Clusters with Bis（tetrazole）amine Ligands

A new metal-organic framework, {Zn[Zn3（BTA）3（μ3-OH）（H2O）3]2}n 1, has been synthesized under hydrothermal reaction of ZnCl2 and bis（5-tetrazolyl）amine （H2BTA）, and characterized by elemental analysis, FT-IR, Raman spectrum, X-ray single-crystal diffraction, TGA and photoluminescence measurements. Compound 1 crystallizes in the trigonal system, space group P-3cl, a = 13.667（3）, c = 12.981（3） A, V = 2099.6（8） A3 and Z = 2. The BTA2- ligand in 1 assumes theμ3 tetradentate mode with both 1,2- and 1,4-tetrazole bridges, generating an unusual 2-D layer, in which the [Zn3（μ3-OH）] triangular motifs act as three-connecting nodes and the mononuclear Zn atoms as six-connecting nodes that are inter-linked by organic ligands. Adjacent 2-D metal-organic layers are linked by strong hydrogen bonds to form a novel 3-D supramolecular framework. Complex 1 exhibits blue fluorescence emission in the solid state at ambient temperature.     

Synthesis and Structure of a Novel Supramolecular Compound E Co（ 2,2＇-bipy） （ H20 ） 4] E trans-1,4-chdc ] and Separation of Isomer of 1,4-Cyclohexanedicarboxylic Acid

A supramolecular compound, [ Co（2,2＇-bipy） （ H2O）4 ] [ trans-1,4-chdc ] （ compound 1 ） （ 2,2＇-bipy = 2,2＇- bipyridine, 1,4-chdcH2 = 1,4-cyclohexanedicarboxylic acid）, was synthesized and characterized by single-crystal Xray diffraction analysis, IR spectrometry, TG analysis, and elemental analyses. Single-crystal X-ray diffraction analysis revealed that [ Co（ 2,2＇-bipy） （ H2O）4 ]^2＋ units and adjacent 1,4-chdc^2- formed a single layer by hydrogen bonding and electrostatic interactions along the ac-plane, and two symmetry-related single layers interacted with each other by hydrogen bonding, resulting in a double layer, which further formed a 3-D structure by π-π stacking. The most attractive structural feature of compound 1 is that 1,4-chdc2- possesses only tram-conformation although there are both c/s- and tram-conformations in the raw material.     

A Novel Two-dimensional Lead(Ⅱ) Coordination Polymer Based on Dinuclear Lead(Ⅱ) Unit Containing(5-Chloro-quinolin-8-yloxy) Acetate

A novel two-dimensional lead(II) coordination polymer 1, [C11H7Cl2NO3Pb]n, has been prepared by solvothermal reaction of new bridging ligand(5-chloro-quinolin-8-yloxy)acetic acid(HL) with PbCl2, and its structure was characterized by IR, elemental analysis, TG-DTA and single-crystal X-ray diffraction analysis. The crystal is of monoclinic system, space group P21/c with a = 16.7603(7), b = 8.6907(4), c = 8.4745(3), β = 101.1110(11)°, C11H7Cl2NO3 Pb, Mr = 479.27, V = 1211.25(9)3, Z = 4, Dc = 2.628 g/cm3, F(000) = 880, μ = 14.367 mm-1, R = 0.0173 and wR = 0.0508. The asymmetric unit contains one lead(II) cation, one(5-chloro-quinolin-8-yloxy)acetate(L) ligand and a chloride ion. The PbII center is hepta-coordinated in a distorted pentagonal bipyramidal geometry. The coordination sphere of the Pb atom is completed by two oxygen atoms and one nitrogen atom of the same L ligand, two bridging chloride ions and two bridging oxygen atoms of two adjacent L ligands. Two PbII centers are linked by the two L ligands to form a C2-symmetric dimer unit with a planar [Pb2O2] ring. Each dimer unit acts as a secondary building unit(SBU) and links adjacent four dimer units by the chloride atoms and oxygen atoms of carboxylate groups of L, forming a two-dimensional array. Such two-dimensional layers are packed through intermolecular C–H···Cl hydrogen bonds into a three-dimensional supramolecular structure. When the dimer unit is viewed as a 4-connected node, 1 is simplified as a 4-nodal 2-D network with square lattices of the diagonal lengths to be 6.079(1). The fluorescence emission peak of complex 1 appears near 407 nm.     

Crystal Structure of a Cu（Ⅱ） Coordination Polymer： [Cu（IP）（TBZH）]2n （TBZH = Thiabendazole,IP = Isophthalic Acid）

The structure of a copper（Ⅱ） polymer, [Cu（IP）（TBZH）]2n 1 （TBZH = thiabendazole, IP = isophthalic acid）, has been determined by X-ray crystallography and characterized by elemental analysis, IR spectrum and thermogravimetric analysis. It crystallizes in the monoclinic system, space group P21/n with a = 11.76, b = 10.41, c = 14.08A^°, β = 104.80°, V= 1666.0（3）A^°^3, Z = 4, Mr= 428.90, Dc= 1.710 g/cm^3, F（000） = 868,μ = 1.468 mm^-1 and S = 1.001. The 2-D layered gridding architecture of 1 is constructed from isophthalic acid and binuclear copper atoms. Hydrogen bonds and aryl ring π-π stacking interactions in 1 contribute to a supramolecular structure.     

Structures and Photoluminescent Properties of Two Complexes Based on Dipyrido[3,2-a:2?,3?-c]phenazine and 2,4?-Biphenyldicarboxylic Acid

ABSTRAC Two new complexes [Cd(2,4?-bpdc)(DPPZ)]_(2n)·n H_2O(1) and [Zn(2,4?-Hbpdc)_2(DPPZ)]· H_2O(DPPZ = dipyrido[3,2-a:2?,3?-c]phenazine, 2,4?-H_2bpdc = 2,4?-biphenyldicarboxylic acid) have been hydrothermally synthesized. The structure of complex 1 was determined by single-crystal X-ray diffraction diffraction and further characterized by elemental analysis, IR spectrum, powder X-ray diffraction(XRD) and single-crystal X-ray diffraction. Complex 1 has 1D chains, which are further connected by π-π stacking interactions of neighbouring chains, generating a steady 3D supramolecular structure. Complex 2 shows the isolated mononuclear units, which are further extended to a 2D supramolecular layered structure through π-π stacking interactions and hydrogen bonds. Furthermore, complexes 1 and 2 exhibit green photoluminescent properties at room temperature.     

Syntheses, Structures and Luminescent Properties of Two Zinc Complexes Containing N-P-Acetamidobenzenesulfonyl-glycine Acid Ligand

Using N-P-acetamidobenzenesulfonyl-glycine acid （abbreviated as abglyH2） as a ligand, two zinc（II） complexes [Zn（abglyH）2（bipy）2（H2O）2], （1） and {[Znz（abgly）2（bipy）2（H2O）2]. 2（H2O）}n （2） （bipy = 4,4＇-bipyridine） have been synthesized under mild conditions and characterized by IR, elemental analysis and X-ray diffraction analysis. Complex 1 is a monomeric compound, which is further assembled by intermolecular hydrogen bonds and π-π interactions into a 3-D supramolecular network. Complex 2 adopts a one-dimensional double chain structure and is further linked by hydrogen bonds to form a 2-D structure. Fluorescent analysis shows that complex 1 has an emissive maximum at 337 nm and complex 2 exhibits an emissive maximum at 339 nm in the solution state at room temperature.     

Two New Copper(Ⅱ) Complexes with p-Cyanobenzoic Acid: Synthesis,Crystal Structures and Properties

The complexes of [Cu(bpy)(H2O)(CBA)2]n 1 and [Cu(phen)(H2O)(CBA)2]·H2O 2 based on p-cyanobenzoic acid(HCBA) have been synthesized in aqueous ethanolic solution at room temperature. The single-crystal X-ray diffraction studies demonstrated that complex 1 crystallizes in orthorhombic and complex 2 is of triclinic system. The results indicate the complex 1 shows a 1D chain structure bridged by two carboxylic oxygen atoms from CBA–, and complex 2 is a mononuclear structure. Through intermolecular hydrogen bonding and π...π stacking interactions, the complexes are assembled into supramolecular structures. Complex 1 has been characterized by magnetic measurements. The magnetic measurement indicates that weak ferromagnetic interaction(zJ= 0.038(5)) between the Cu2+ ions is dominant in the structure. The IR spectrum and results of thermal and elemental analyses are also presented.     

Syntheses and Crystal Structures of Copper(II) and Silver Complexes with 5‐Methyl‐1‐(4‐Methylphenyl)‐1,2,3‐Triazol‐4‐Carboxylic Acid

Two novel complexes [Cu L ₂(MeOH)] ( 1 )and [Ag₂ L (H L )₂(MeOH)] ( 2 ) ( L = 5‐methyl‐1‐(4‐methylphenyl)‐1,2,3‐triazol‐4‐carboxylic acid) were synthesized and characterized by elemental analysis, IR and X‐ray diffraction. Complex 1 is a mononuclear structure; the molecules were assembled into an infinite 2–D supramolecular by the C–H···O weak interactions. Complex 2 is a centrosymmetric dinuclear structure with bis(unidentate) carboxylato co‐ordination mode, and the molecules were assembled into 2–D layers by C–H···O and O–H···O weak interactions.     

Syntheses and Characterization of Two Coordination Polymers Constructed by the Ligand 3,5‐Bis(pyridin‐4‐ylmethoxy)benzoic Acid

Two coordination polymers, namely [Zn(L1)(OAc)]·H₂O ( 1 ) and [Cd(L1)₂] ( 2 ), where L1 = 3,5‐bis(pyridin‐4‐ylmethoxy)benzoic acid, have been synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction analysis. Complex 1 has a 2D layer structure in which the hydrogen bonds between lattice water molecules and uncoordinated carboxylate oxygen atoms of the ligand L1 in the adjacent layers extend the 2D layer into a 3D supramolecular architecture. The structure of 2 is a 2D (3,5)‐connected net with (3·5²)(3²·5³·6⁴·7) topology. In addition, the luminescent properties of complexes 1 and 2 have been studied in the solid state at room temperature.     

基于顺丁烯二酸和N,N螯合配体构筑的两个新型三维氢键型超分子体系: 结构、磁性质与理论化学研究

通过调变辅助配体,设计合成了两个新的Cu(II)化合物Cu(mal)(tap)(H2O)]n(1) 和 [Cu2(mal)2(bpym)2(H2O)2]·2H2O(2) (其中H2mal =顺丁烯二酸, tap=1,4,5,8-四氮杂菲,bpym=2,2′-联嘧啶),并用X-射线单晶衍射技术对其进行了结构表征。化合物1是一维弓背状配位聚合链通过氢键和π–π 堆积作用拓展形成的三维超分子体系;化合物2 展现一个具有六连接α-Po(46)拓扑的3D→3D二重穿插结构。此外根据晶体结构,利用Gaussian 03W中的DFT方法对化合物1和2进行几何构型优化,同时,用DFT-BS方法研究了两个化合物的磁性,结果表明计算结果与实验结果吻合,它们均具有弱的反铁磁相互作用。     

Synthesis,Structures, and Catalytic Properties of Two ­Cobalt(II) Coordination Polymers Based on 5‐Substituted Isophthalate and Flexible Bis(benzimidazole) Co‐ligands

Two new Co^II coordination polymers, [Co(L₁)_0.5(hip)]_n ( 1 ) and [Co(L₂)(mip) · 2H₂O]_n ( 2 ) [L₁ = 1,1′‐(1,4‐butanediyl)bis‐1H‐benzimidazole, L₂ = 1,3‐bis(5,6‐dimethylbenzimidazol‐1‐yl)‐2‐propanol, H₂hip = 5‐hydroxyisophthalic acid, H₂mip = 5‐methylisophthalic acid], were synthesized under hydrothermal conditions and structurally characterized by elemental analysis, IR spectroscopy, and X‐ray single‐crystal diffraction. Complex 1 exhibits a 3D supramolecular network constructed with 2D (4,4) layer by O–H ··· O hydrogen bonding. Complex 2 has 1D ladder‐like chains, which are further assembled into a 3D supramolecular framework by π–π stacking interactions. In addition, fluorescence and catalytic properties of compounds 1 and 2 were investigated in solid state.     

Synthesis and Characterization of Three Diverse Coordination Frameworks under Co-ligand Intervention

The chelating organic ligands of 2,2’-bipyridine (2,2’-bipy), di(pyrid-2-yl)amine (dpa) and 2,6-di(pyrid-2-ylamino)pyridine (dpap) were respectively applied to react with H2fum (fumaric acid) and copper salts, affording three different complexes [Cu2(fum)(2,2’-bipy)4]•2ClO4 (1), [Cu2(µ-OH)2(fum)(dpa)2]•2H2O (2) and [Cu(SO4)(H2O)(dpap)]•H2O (3). These complexes were determined by single-crystal X-ray diffraction. Each penta-coordinated Cu(II) ion exhibits a distorted trigonal bipyramidal geometry in 1. The fum ligand links copper ions to form a dinuclear copper unit. While in 2, the fum ligands connect [Cu2(µ-OH)2(dpa)2] unit to construct a 1D zigzag chain. Unexpectedly, when dpap instead of dpa was used under the same conditions, only one mononuclear complex 3 was formed. Crystal packings show that 1—3 form 3D supramolecular architectures through non-covalent interactions (multiple hydrogen bonds and C—H…π/π-π interactions). In addition, the study of the magnetic property reveals dominating ferromagnetic interactions between Cu(II) atoms in 1.     

Di‐μ‐iodo‐bis{[1,1′‐methyl­enebis(3,5‐dimethyl‐1H‐pyrazole‐κN2)]copper(I)}

In the title compound, [Cu₂I₂(C₁₁H₁₆N₄)₂], each of the two crystallographically equivalent Cu atoms is tetrahedrally coordinated by two N atoms from one 1,1′‐methyl­ene­bis(3,5‐di­methyl‐1H‐pyrazole) ligand and two bridging iodide anions. The mol­ecule has a crystallographic center of symmetry located at the mid‐point of the Cu·Cu line. One H atom of the CH₂ group of the 1,1′‐methyl­ene­bis(3,5‐di­methyl‐1H‐pyrazole) ligand interacts with an iodide ion in an adjacent mol­ecule to afford pairwise intermolecular C—H·I contacts, thereby forming chains of mol­ecules running along the [101] direction.     

Syntheses,Structures, and Electrochemical Properties of Two Bis‐triazole‐bis‐amide‐based Copper(II) Pyridine‐2,3‐dicarboxylate Coordination Polymers

Abstract. Two bis‐triazole‐bis‐amide‐based copper(II) pyridine‐2,3‐dicarboxylate coordination polymers (CPs), [Cu(2,3‐pydc)(dtb)_0.5(DMF)] · 2H₂O ( 1 ) and [Cu(2,3‐pydc)(dth)_0.5(DMF)] · 2H₂O ( 2 ) (2,3‐H₂pydc = pyridine‐2,3‐dicarboxylic acid, dtb = N,N′‐bis(4H‐1,2,4‐triazole)butanamide, and dth = N,N′‐bis(4H‐1,2,4‐triazole)hexanamide), were synthesized under solvothermal conditions. CPs 1 and 2 show similar two‐dimensional (2D) structures. In 1 , the 2,3‐pydc anions bridge the Cu^II ions into a one‐dimensional (1D) chain. Such 1D chains are linked by the dtb ligands to form a 2D layer. The adjacent 2D layers are extended into a three‐dimensional (3D) supramolecular architecture by hydrogen‐bonding interactions. The electrochemical properties of 1 and 2 were investigated.     

Syntheses,Crystal Structures,and Photocatalytic Activities of Three Copper Coordination Polymers Based on Bis(1H‐imidazol‐4‐yl)benzene/3‐(2‐Pyridyl)pyrazole

Three copper(II) coordination polymers (CuCPs), namely, [Cu_0.5(1,4‐bib)(SO₄)_0.5]_n ( 1 ), {[Cu(1,3‐bib)₂(H₂O)] · SO₄ · H₂O}_n ( 2 ), and [Cu(bpz)(SO₄)_0.5]_n ( 3 ), were assembled from the reaction of three N‐donors [1,4‐bib = 1,4‐bis(1H‐imidazol‐4‐yl)benzene, 1,3‐bib = 1,3‐bis(1H‐imidazol‐4‐yl)benzene, and Hbpz = 3‐(2‐pyridyl)pyrazole] with copper sulfate under hydrothermal conditions. Their structures were determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses (EA), IR spectroscopy, powder X‐ray diffraction (PXRD), and thermogravimetric analyses (TGA). Structure analyses reveal that complex 1 is a 3D 6‐connected {4¹² · 6³}‐ pcu net, complex 2 is a fourfold 3D 4‐connected 6⁶‐ dia net, whereas complex 3 is a 1D snake‐like chain, which further expanded into 3D supramolecular architectures with the help of C–H ··· O hydrogen bonds. Moreover, the photocatalytic tests demonstrate that the obtained CuCPs are photocatalysts in the degradation of MB with the efficiency is 86.4 % for 1 , 75.3 % for 2 , and 91.3 % for 3 after 2 h, respectively.     

C—H…Cl Hydrogen Bond and π-π Interaction Based Two 3D Supramolecular Architectures of Cu(II) and Co(II) Complexes with Chiral 1,2-Bis(benzimidazol-2-yl) ethane Ligand Containing 2D Grids

合成了两个新的配合物CuLCl₂•2EtOH(1) 和CoLCl₂ (2) [L是( S , S )－1,2－二N－甲基苯并咪唑－1,2－二甲氧基－乙烷],并通过单晶X衍射确定它们的结构。配合物1中,L作为三齿[N, N, O]配体,而配合物2 中,L作为二齿[N, N]配体。这两个配合物共同的结构特点都是通过分子内氢键形成2维的格子结构,然后通过分子间的C－H···Cl型氢键和π–π堆积作用形成3维结构。