Three cobalt(II) coordination polymers constructed from flexible bis(thiabendazole) and dicarboxylate linkers: crystal structures,fluorescence, and photocatalytic properties

Three Co(II) coordination polymers, namely, {Co(btbb)_0.5(ndc)(H₂O)}_n (1), {[Co(btbb)(bpdc)]·1.5H₂O}_n (2), and {[Co(btbp)₂(3-npa)]·2H₂O}_n (3) (btbb = 1,4-bis(thiabendazole)butane, btbp = 1,3-bis(thiabendazole)propane, H₂ndc = 2,6-naphthalenedicarboxylic acid, H₂bpdc = 4,4′-biphenyldicarboxylic acid and 3-H₂npa = 3-nitro phthalic acid) were synthesized under hydrothermal conditions. Their X-ray crystal structures show that complexes 1 and 2 both have 2D uninodal 3-connected hcb (honeycomb) structures. Complex 1 is further extended into a threefold interpenetrating 3D 4,4-connected mog (moganite) supramolecular architecture with the point symbol of {4.6⁴.8}₂{4².6².8²} by O–H···O hydrogen bonding interactions. Complex 2 shows a 3D supramolecular framework involving π···π stacking interactions. Complex 3 features a uninuclear structure, which is further assembled into an ordered 2D hydrogen-bonded-driven pattern with O–H···O and O–H···N hydrogen bonding interactions. The fluorescence spectra and photocatalytic properties of complexes 1–3 for degradation of methyl orange were investigated.     

Cobalt(II) and silver(I) coordination polymers constructed from flexible bis(5,6-dimethylbenzimidazole) and substituted isophthalate co-ligands

Two coordination polymers, [Co(L1)(IPA] _n (1) and {[Ag(L2)(HMIPA)]·H₂O} _n (2) (H₂IPA = isophthalic acid, L1 = 1,2-bis(5,6-dimethylbenzimidazol-1-ylmethyl)benzene, H₂MIPA = 5-methylisophthalic acid, L2 = 1,6-bis(5,6-dimethylbenzimidazol-1-yl)hexane, have been synthesized and characterized by physicochemical and spectroscopic methods, as well as single-crystal X-ray diffraction. In 1, six-coordinated cobalt centers are bridged by L1 and IPA^2? ligands to generate a (4,4) two-dimensional layer. However, complex 2 features a 1D chain structure, which is further extended by O–H···O hydrogen bonding interactions into a 2D supramolecular layer with (6³) topology. The fluorescence and thermal gravimetric analysis of both complexes were also explored. Furthermore, the complexes 1 and 2 exhibit remarkable catalytic properties for the degradation of methyl orange dyes in a Fenton-like process.     

Hydrothermal syntheses,crystal structures,and properties of two new coordination polymers constructed from a flexible pyridinecarboxylate ligand

Two new coordination polymers with the same topological structure [Zn(L)]_2n·n(H₂O) (1) and [Co(L)]_2n·n(H₂O) (2) (H₂L = 5-(pyridin-2-ylmethoxy)-isophthalic acid) have been hydrothermally synthesized by reactions of metal salts and H₂L. Single-crystal X-ray analyses reveal that 1 and 2 are isostructural and crystallize in orthorhombic chiral P2₁2₁2 space group. These compounds feature 2-D undulated layer structures with (3,6)-connected kgd topology, which further extended into a 3-D supramolecular framework via intermolecular hydrogen bonds. In addition, the luminescent properties of 1 and 2 and the magnetic property of 2 were also investigated.     

Copper(II) coordination polymers constructed from aromatic polycarboxylate and flexible triazole ligands with different spacer lengths: syntheses,structures, and properties

{[Cu₂(btm)₂(Hbtc)(H₂btc)₂(H₂O)]·9.5H₂O}_n (1), [Cu(bte)(H₂btc)₂]_n (2) {[Cu(btp)(H₂btc)₂]·0.25H₂O}_n (3) (btm?=?bis(1,2,4-triazol-1-yl)methane, bte?=?bis(1,2,4-triazol-1-yl)ethane, btp?=?bis(1,2,4-triazol-1-yl)propane, H₃btc?=?benzene-1, 3, 5-tricarboxylic acid) have been synthesized and structurally characterized. 1 features a 1-D double chain, which is interconnected by classical hydrogen-bonding (O–H?O) and π–π interactions to lead to a 3-D supramolecular architecture. 2 and 3 are both 1-D single chains, which are interconnected by π–π interactions to 2-D layer architectures. Elemental analysis, XRD, IR, TG and EPR spectra have been carried out and discussed.     

One- and two-dimensional cobalt(II) coordination polymers derived from flexible bis(benzimidazole) and aromatic carboxylate co-ligands

Two new coordination polymers, formulated as [Co(L1)(btec)_0.5] _n (1) and {[Co(L2)(bdc)]·H₂O} _n (2) (L1 = 1,3-bis(2-methylbenzimidazol-1-ylmethyl)benzene, H₂bdc = 1,3-benzenedicarboxylic acid, H₄btec = 1,2,4,5-benzenetetracarboxylic acid, L2 = 1,3-bis(benzimidazol-1-ylmethyl)benzene), have been hydrothermally synthesized and characterized by physicochemical and spectroscopic methods as well as single-crystal X-ray diffraction. The cobalt atoms present different environments, with a trigonal pyramidal geometry in 1 and a distorted octahedral configuration in 2. Complex 1 shows a 2D (4,4) network linked by L1 and btec^4? anions, giving an uninodal 4-connected sql topology with a point symbol of {4²·6²}, while complex 2 displays a 1D ladder-like chain structure, which is further assembled into a 3D supramolecular architecture via C–H···π hydrogen bonding interactions. The fluorescence properties of both complexes have been investigated in the solid state.     

Zinc(II) and manganese(II) coordination polymers constructed by 2-naphthyl imidazole dicarboxylate: syntheses,structures and properties

Three coordination polymers [Zn(μ₃-HNIDC)(CH₃OH)]_n (H₃NIDC = 2-(2-naphthyl)-1H-imidazole-4,5-dicarboxylic acid) (1), [Mn(μ₂-HNIDC)(4,4′-bipy)]_n (4,4′-bipy = 4,4′-bipyridine) (2) and [Mn₂(μ₂-HNIDC)₂(phen)₂]_n (phen = 1,10-phenanthroline) (3) have been solvothermally synthesised and structurally characterised by single-crystal X-ray diffraction, elemental analyses, thermal analyses and IR spectra. Polymer 1 displays a three-dimensional open architecture with one-dimensional (1D) channels. Polymer 2 exhibits a sheet structure containing infinite rectangles. Polymer 3 presents a 1D wave chain structure. The solid-state photoluminescence of 1 has been investigated as well.     

Synthesis, crystal structures and catalytic properties of copper(II) and cobalt(II) coordination polymers based on a flexible benzimidazole ligand

Two coordination polymers, namely [Cu(L)₂]·(NO₃)₂ (1) and [Co(L)(chdc)]·2H₂O (2) [(chdc?=?1,4-cyclohexanedicarboxylate, L?=?1,3-bis-(5,6-dimethylbenzimidazole-1-yl-methylene)-benzene], based on a flexible 5,6-dimethylbenzimidazole ligand have been synthesized and characterized by physico-chemical and spectroscopic methods and single-crystal diffraction. Complex 1 shows a 2D (4,4) network structure linked by L ligands while complex 2 displays a 1D ladder-like chain bridged by L and chdc ligands. The catalytic activities of both complexes for the degradation of methyl orange have been investigated.     

Two d 10-metal coordination polymers constructed from flexible ligands: Syntheses, crystal structures, and luminescent properties

Two new complexes, Zn(Glut)(Bix) · 2H₂O (I) and Cd(Pda)(Bimb) (II) (H₂Glut = glutaric acid, H₂Pda = 1,3-phenylenediacetic acid, Bix = 1,4-bis(imidazol-1-ylmethyl)benzene and Bimb = 1,4-di(1H-imidazol-1-yl)butane) were obtained under hydrothermal conditions by employing mixed ligands with metal salts and characterized by elemental analysis, IR, TGA, and Single crystal X-ray diffraction. Complex I presents a two-dimensional 2-fold interpenetrating layer structure. Whereas complex II is a two-dimensional layer network and exhibits a typical (4,4) topological net. The infrared spectra, thermogravimetric and luminescent properties were also investigated in detail for two complexes.     

Synthesis, crystal structures and catalytic properties of two 1D cobalt(II) coordination polymers

Two new cobalt(II) coordination polymers, namely [Co_1.5(PhCOO)₃(bbbm)_1.5(H₂O)] _n (1) and [Co(chdc)(bbbm)] _n (2) (bbbm = 1,1′-(1,4-butanediyl)bis-1H-benzimidazole, H₂chdc = 1,4-cyclohexanedicarboxylic acid), have been synthesized and structurally characterized by single crystal X-ray diffraction. The cobalt(II) centers display different environments, with trigonal–bipyramidal and octahedral geometries in 1 and a tetrahedral geometry in 2. The 1D linear chains of complex 1 and ladder-like chains of complex 2 are bridged by bbbm in bis-monodentate coordination mode; the variation of the carboxylate co-ligand effectively tunes the resulting framework architecture. The degradation of methyl orange in a photochemical Fenton-like process using complexes 1 and 2 as catalysts was investigated.     

Hydrothermal syntheses,crystal structures and properties of two cobalt(II) complexes constructed from 5-(isonicotinamido)isophthalic acid

Two Co(II) complexes, [Co(INAIP)(dib)]·4H₂O and [Co(INAIP)(phen)(H₂O)]·H₂O have been synthesized by the reaction of 5-(isonicotinamido)isophthalic acid (H₂INAIP) and CoSO₄·7H₂O, as well as N-donor ligands, namely 1,4-di(1-imidazolyl)benzene (dib) and 1,10-phenanthroline (phen) under hydrothermal conditions. Single-crystal X-ray diffraction analysis indicates that [Co(INAIP)(dib)]·4H₂O has a two-dimensional (2D) double-layer network structure with a (4, 4) topology, while [Co(INAIP)(phen)(H₂O)]·H₂O displays a one-dimensional chain structure, extending to a 2D net through the π–π interactions. In addition, the photoluminescence and degradation of methyl orange in a Fenton-like process using the complexes as catalysts were investigated.     

不同V型辅助配体构筑的两个镉配位聚合物的合成、结构和荧光性质

在溶剂热条件下,合成了2个基于V型辅助配体（bipmo、bppmo）的镉配位聚合物{[Cd （bipmo）（NDC）]·1.75H₂O}_n（1）和{[Cd （bppmo）（NDC）（H₂O）]·H₂O}_n（2）,其中H₂NDC=2,6-萘二羧酸,bipmo=双（4-（1H-咪唑-1-基）苯基）甲酮,bppmo=双（4-（吡啶-4-基）苯基）甲酮。利用单晶X射线衍射、键价和分析、红外光谱和元素分析对其结构进行了表征。研究发现,配合物1具有二重互穿的{6³}拓扑结构。配合物2同样是3-连接的{6³}拓扑,却存在三重穿插结构。分析表明,V型配体对最终结构的形成有很大影响。此外,对配合物1和2的发光性质也进行了详细研究。     

不同V型辅助配体构筑的两个镉配位聚合物的合成、结构和荧光性质

在溶剂热条件下,合成了 2 个基于 V 型辅助配体(bipmo、bppmo)的镉配位聚合物{[Cd(bipmo)(NDC)]·1.75H₂O}_n (1)和{[Cd(bppmo)(NDC)(H₂O)]·H₂O}_n (2),其中 H2NDC=2,6 萘二羧酸,bipmo=双(4 (1H 咪唑 1 基)苯基)甲酮,bppmo=双(4 (吡啶 4 基)苯基)甲酮。利用单晶X射线衍射、键价和分析、红外光谱和元素分析对其结构进行了表征。研究发现,配合物1具有二重互穿的{63}拓扑结构。配合物2同样是 3 连接的{6³}拓扑,却存在三重穿插结构。分析表明,V型配体对最终结构的形成有很大影响。此外,对配合物1和2的发光性质也进行了详细研究。     

三个含5-(4-羧基苯氧基)烟酸配体的锌(II)、钴(II)和镍(II)配位聚合物的合成、晶体结构及催化性质

采用水热方法,选用配体 5-(4-羧基苯氧基)烟酸(H₂cpna)与 1,2-二(4-吡啶基)乙烷(dpea)或 1,2-二(4-吡啶基)乙烯(dpey)分别与ZnCl₂、CoCl₂·6H₂O和NiCl₂·6H₂O在160 ℃温度下反应,合成了3个配位聚合物：[Zn(μ₃-cpna)(μ-dpea)_0.5]_n (1)、[Co(μ₃-cpna)(μ-dpey)_0.5]_n (2)和[Ni(μ₃-cpna)(μ-dpey)_0.5(H₂O)]_n (3)。这些配合物为稳定的结晶固体,我们通过红外光谱、元素分析、热重分析和单晶X射线衍射分析对其进行了表征。单晶X射线衍射分析表明,3个配合物的晶体属于三斜晶系P$overline{1}$空间群。配合物1~3呈二维层状结构。我们考察了这些配合物在 Knoevenagel缩合反应中的催化活性。研究表明,配合物 1和2在室温下对 Knoevenagel缩合反应表现出有效的催化活性。同时对反应参数进行了优化,对底物范围也进行了研究。     

Manganese(II), nickel(II), and cadmium(II) coordination polymers with tetrafluoroterephthalate: syntheses,crystal structures,and luminescence properties

Three new coordination polymers, [Mn(BDC-F₄)(DMF)₂(H₂O)₂] _n (1), [Ni(BDC-F₄)(DMF)(EtOH)] _n (2), and [Cd(BDC-F₄)(DMF)(EtOH)] _n (3), have been synthesized by assembling transition metal salts with the rigid ligand tetrafluoroterephthalic acid (H₂BDC-F₄) in mixed EtOH/DMF solvent at pH ca. 2. For complex 1, the octahedral coordination geometry of the Mn^II center is provided by two oxygen atoms from two dianionic BDC-F₄ ligands, two DMF ligands and two aqua ligands, giving a 1-D linear chain array. For complex 2, the Ni^II center is coordinated by two dianionic BDC-F₄ ligands, two EtOH ligands and two DMF ligands, resulting in a 1-D chain structure. For complex 3, the Cd^II center is coordinated by four dianionic BDC-F₄ ligands, one EtOH ligand and one DMF ligand, generating a 2-D layered structure. The results suggest that both the metal and the solution pH play an important role in the formation of the complexes. The spectroscopic, thermal, and luminescence properties of the complexes have been investigated.     

One-dimensional and two-dimensional coordination polymers constructed from copper(II) nodes and polycarboxylato spacers: Synthesis,crystal structures and magnetic properties

Four new coordination polymers were obtained by employing polycarboxylato spacers and cationic copper(II) complexes as nodes: ^∞₂[Cu₃(trim)₂(NH₃)₆(H₂O)₃] (1); ^∞₁[Cu(tmen)(dhtp)] (2), ^∞₁[Cu(tmen)(hitp)(H₂O)] (3), ^∞₁[Cu(tmen)(nitp)] (4). (H₃trim = trimesic acid, H₂dhtp = 2,5-dihydroxy-terephthalic acid; H₂hitp = 5-hydroxy-isophthalic acid, H₂nitp = 5-nitro-isophthalic acid; tmen = N,N,N′,N′-tetramethyl-ethylenediamine). The crystal structures of the four compounds have been solved. Compound 1 consists of 2D coordination polymers with heart-shaped meshes, while compounds 2–4 contain infinite zigzag chains. The role of the hydrogen bond interactions in sustaining the supramolecular solid-state architectures in compounds 1 and 3 is discussed. The cryomagnetic investigation of compounds 1, 2, and 4 reveals antiferromagnetic interactions between the copper ions.     

Syntheses, crystal structures and properties of two nickel(II) coordination polymers constructed from 5-(isonicotinamido)isophthalic acid

Two Ni(II) metal–organic frameworks, [Ni(INAIP)(DMF)]·0.5DMF and [Ni(INAIP)(H₂O)]·2H₂O, have been synthesized by the reaction of 5-(isonicotinamido)isophthalic acid (H₂INAIP) with NiSO₄·6H₂O using different reaction solvents. Single-crystal X-ray diffraction analysis indicates that [Ni(INAIP)(DMF)]·0.5DMF has a twofold interpenetrated three-dimensional (3D) framework with sra topology, while [Ni(INAIP)(H₂O)]·2H₂O has a two-dimensional (2D) network structure with a 4-connected (4³·6³) topology. In addition, the magnetic and adsorption properties of the complexes were explored.     

Diverse topologies of three cobalt(II) coordination polymers constructed from flexible bis(benzimidazole) and dicarboxylate ligands

Three cobalt(II) coordination polymers {[Co(L1)(nda)(H₂O)₂]·2H₂O} _n (1), [Co(L2)(tbi)(H₂O)] _n (2) and [Co(L2)(bpdc)(H₂O)] _n (3) (L1 = 1,3-bis(5,6-dimethylbenzimidazol-1-yl)-2-propanol, L2 = 1,3-bis(benzimidazol-1-yl)-2-propanol, H₂nda = 2,6-naphthalenedicarboxylic acid, H₂tbi = 5-tert-butyl isophthalic acid and H₂bpdc = 4,4′-biphenyldicarboxylic acid) were synthesized and characterized by physicochemical and spectroscopic methods. Complex 1 exhibits a 1D loop-like structure, which is further extended into a 3D 3,3,4T31 network through two O–H···O hydrogen bonding interactions. Complex 2 displays a 1D ladder-like chain, arranged into a 2D supramolecular network with 3,3,4L34 topology via classical O–H···O hydrogen bonding interactions, whereas complex 3 features a 2D 3,4L13 layer structure and further assembles into a 3D framework with a twofold interpenetrating sqc65 topology through O–H···O hydrogen bonding interactions. The fluorescence and catalytic properties of these complexes for the degradation of Congo red in a Fenton-like process have been investigated.