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.     

Two zinc (II) coordination polymers based on aliphatic ether Schiff base: Synthesis,crystal structure,antioxidation and fluorescence

The synthesis of two 1D coordination polymers [Zn₂L¹₂]_n 1 and [Zn₂L²₂]_n 2 , based on the H₂L¹ (bis (salicylidene)‐3‐oxapentane‐1,5‐diamine) and the H₂L² (bis (5‐methylsalicylaldehyde)‐3‐oxapentane‐1,5‐diamine) ligands, have been described and characterized by IR, elemental analysis and X‐ray single crystal analyses. In coordination polymer 1 , each Zn²⁺ ion is five‐coordinated by three oxygen atoms and two nitrogen atoms from deprotonated ligand forming a square pyramidal configuration. It is worth noting that phenolic oxygens of the deprotonated H₂L¹ adapt monodentate and monoatomic bridging coordinated modes resulting in one‐dimensional linear chain structure in which macro rings alternately connect small rings. The coordination polymer 2 is a four‐coordinated one‐dimensional zigzag chain in which geometric structure around the Zn (II) atom can be described as distorted tetrahedron. The antioxidant activity of the coordination polymers 1 – 2 and the ligands were determined by superoxide and hydroxyl radical scavenging method in vitro. The results demonstrated that the coordination polymers exhibit more effective antioxidant activity than the ligands. Moreover, compared with emissive bands of the free ligands in the solid state and DMF solvent, the photoluminescent transition of the Zn (II) coordination polymer 1 – 2 may be attributed to ligand‐to‐ligand charge‐transfer regulated by Zn (II) ion.     

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。     

Two novel trinuclear cluster-based coordination polymers with 2,6-Di-imidazol-1-yl-pyridine: solvothermal syntheses,crystal structures,properties and Hirshfeld surface analysis

Two novel trinuclear cluster-based coordination polymers {[M₃(dip)(AcO)₆]·(X)}_n (1, M = Cu, X = CH₃OH; 2, M = Co, X = 2H₂O) (dip is 2,6-Di-imidazol-1-yl-pyridine), have been synthesised and structurally determined by single crystal X-ray diffraction, element analysis. Crystallographic unit of 1 consists of three Cu(II), six acetic ions, one dip ligand and one methanol molecule, which formed 1D chain through acetic bridges. The 1D chain further constructed 2-D network through dip ligand bridge which formed 3-D network through π···π interaction. Crystallographic unit of 2 consists of three Co(II), six acetic ions, one dip ligand and two water molecules. The trinuclear unit further formed a dimmer through dip ligand bridge which constructed 1-D through dip ligand bridge. The 1D chain further constructed 2-D network through π···π interaction. IR and UV–vis spectrum properties of 1 and 2 were studied. In addition, Hirshfeld surface analysis was also studied for 1.     

A twofold interpenetrating two‐dimensional zinc(II) coordination polymer: synthesis,crystal structure and physical properties

A novel twofold interpenetrating two‐dimensional (2D) Zn^II coordination framework, poly[[(μ‐1,3‐bis(2‐methyl‐1H‐imidazol‐1‐yl)benzene‐κ²N³:N³)(μ‐naphthalene‐2,6‐dicarboxylato‐κ²O²:O⁶)zinc(II)] dimethylformamide monosolvate], {[Zn(C₁₂H₆O₄)(C₁₄H₁₄N₄)]·C₃H₇NO}_n or {[Zn(1,3‐BMIB)(NDC)]·DMF}_n (I), where H₂NDC is naphthalene‐2,6‐dicarboxylic acid, 1,3‐BMIB is 1,3‐bis(2‐methyl‐1H‐imidazol‐1‐yl)benzene and DMF is dimethylformamide, was prepared and characterized through IR spectroscopy, elemental analysis, thermal analysis and single‐crystal X‐ray diffraction. Single‐crystal X‐ray diffraction analysis revealed that (I) exhibits an unusual twofold interpenetrating 2D network. In addition, it displays strong fluorescence emissions and a high photocatalytic activity for the degradation of Rhodamine B (RhB) under UV‐light irradiation.     

Two new cadmium(II) coordination polymers based on imidazole‐containing ligands: synthesis,structural characterization and fluorescence properties

The judicious selection of suitable ligands is vitally important in the construction of novel metal–organic frameworks (MOFs) with fascinating structures and interesting properties. Recently, imidazole‐containing multidentate ligands have received much attention. Two new Cd^II coordination frameworks, namely, poly[tris{μ‐1,4‐bis[(1H‐imidazol‐1‐yl)methyl]benzene‐κ²N³:N^3′}tetrakis(nitrato‐κ²O,O′)dicadmium], [Cd₂(NO₃)₄(C₁₄H₁₄N₄)₃]_n, (I), and poly[[bis{μ₃‐1,3,5‐tris[(1H‐imidazol‐1‐yl)methyl]benzene‐κ³N³:N^3′:N^3′′}cadmium] hexafluorosilicate], {[Cd(C₁₈H₁₈N₆)₂](SiF₆)}_n, (II), have been synthesized and characterized by elemental analysis, IR spectroscopy and single‐crystal X‐ray diffraction. In polymer (I), the 1,4‐bis[(1H‐imidazol‐1‐yl)methyl]benzene ligand bridges Cd²⁺ ions with a distorted seven‐coordinated pentagonal bipyramidal geometry, forming a one‐dimensional ladder chain, and the nitrate anions coordinate to the Cd²⁺ ions in a terminal bidentate fashion. In the crystal, adjacent chains are further connected by C—H…O hydrogen bonds to generate a two‐dimensional (2D) supramolecular structure. Polymer (II) exhibits a 2D layered structure in which 1,3,5‐tris[(1H‐imidazol‐1‐yl)methyl] benzene ligands join Cd²⁺ centres having a six‐coordinated octahedral structure. The layers are connected by hexafluorosilicate anions via C—H…F hydrogen‐bond interactions, giving rise to a three‐dimensional supramolecular network structure in the solid state. In addition, powder X‐ray diffraction (PXRD) patterns were recorded, thermogravimetric analyses (TGA) carried out and fluorescence properties investigated.     

Syntheses,structural diversity and properties of three coordination polymers built by chlorophenyl imidazole dicarboxylate

Two 2D coordiantion polymers, [Sr(p-ClPhHIDC)(H₂O)]_n (p-ClPhH₃IDC = 2-(4-chlorophenyl)-1H-imidazole-4,5-dicarboxylic acid) (1) and [Cd₃(p-ClPhH₂IDC)₂(p-ClPhHIDC)₂(H₂O)₂]_n (2) and one 3D polymer {[Co₃(p-ClPhHIDC)₃(H₂O)₃]·6H₂O}_n (3) have been prepared successfully under solvothermal conditions and structurally characterised by elemental analyses, IR and XRPD determinations, and have been further analysed by single-crystal X-ray diffraction. Polymer 1 exhibits a graceful 2D grid sheet structure. Polymer 2 can be regarded as a (3,3,4)-coordinated 2D network. Polymer 3 exhibits a 3D motif with 1D open channels and [Co₁₂(p-ClPhHIDC)₉] bihexagonal rings. The coordination features of the newly prepared imidazole dicarboxylate ligand, p-ClPhH₃IDC, have been discussed from both theoretical and experimental aspects. Furthermore, the solid-state photoluminescence and thermal properties of the polymers have also been 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。     

Two 2-dimensional cadmium(II) coordination polymers with 3-amino-5-methylthio-1,2,4-triazolate ligand

Reactions of cadmium(II) salts with 3-amino-5-methylthio-1H-1,2,4-triazole (Hamstz) afforded two cadmium(II) coordination polymers, [Cd₂(amstz)₂Cl₂]_n (1) and [Cd₂(amstz)₂(NO₃)₂]_n (2). Compounds 1 and 2 feature 2-D layered structures based on the dinuclear [Cd₂(amstz)₂] subunits. The cadmium coordination polyhedra are tetrahedral and tetragonal pyramidal in 1 and 2, respectively, due to the presence of different coordinated anions, Cl^? and NO₃^?. Compounds 1 and 2 exhibit photoluminescence emission with maxima at 620 and 621 nm upon excitation at 470 and 472 nm, respectively, which can be attributed to the ligand-to-metal charge transfer emssion.     

Syntheses,structures, and properties of seven-coordinate calcium(II) and five-coordinate lead(II) complexes with 1-D structures

Two new 1-D heterometallic coordination polymers (CPs), {[Ca(NiL)(H₂O)₄]?·?3H₂O} _n (1) and {[Pb(NiL)(H₂O)₂]?·?3H₂O)} _n (2), have been prepared by reactions of CaCl₂ and NiL and Pb(NO₃)₂ and NiL in CH₂Cl₂–H₂O. H₂L denotes dimethyl 5,6,7,8,15,16-hexahydro-6,7-dioxodibenzo-9,10-benzo-[1,4,8,11]tetraazacyclotetradecine-13,18-dicarboxylate. Single-crystal X-ray diffraction studies show that the coordination geometries around Ni(II) in both 1 and 2 are similar distorted N₄ square planar. All Ni–N bonds are short. Complex 1 has 1-D zigzag chain, while 2 shows 1-D “head-to-tail” structure. In crystals 1 and 2, 1-D CP chains were parallel-packed and 3-D supramolecular networks were formed via weak hydrogen bond interactions between aqua ligands and lattice water. The effects of water on the assemblies of the two CPs are discussed. Coordinated water plays an important role on the assembly procedure.     

Syntheses, crystal structures and properties of two 1-D cadmium(II) coordination polymers based on 1,1′-(1,3-propanediyl)bis-1H-benzimidazole

The combination of framework-builders 1,1′-(1,3-propanediyl)bis-1H-benzimidazole (pbbm), Cd(II) ion and framework-regulator ClO₄⁻ or SO₄²⁻ provides two new coordination polymers [Cd(pbbm)₂(ClO₄)₂]_n(1) and {[Cd(pbbm)SO₄(H₂O)₂]·CH₃OH}_n(2). Both of them display 1-D chain framework, but their detailed structures are clearly different from each other. 1 displays a 1-D ribbon of rings framework, 2 features an interesting infinite 1-D looped chain structure composed of two kinds of rings, the smaller 8-membered ring and the larger 20-membered ring. The antimicrobial activities of the two polymers were tested by the agar diffusion method and the results indicated that they exhibited antimicrobial activities against bacterial strands. The measurement of the non-isothermal kinetics of the thermal decomposition of 2 reveals that there are at least three steps that occur in its decomposition process.     

A twofold interpenetrated 3-D Cu(II) coordination polymer based on 5-(pyridin-4-yl)isophthalic acid: synthesis,crystal structure,and magnetic properties

A new copper(II) coordination polymer, [Cu(PIA)·2H₂O]_n (1) [H₂PIA = 5-(pyridin-4-yl)isophthalic acid], has been synthesized and characterized by elemental analysis, IR spectroscopy, TGA, powder, and single-crystal X-ray diffraction. Structural analysis shows that each PIA^2? in 1 bridges three Cu(II) ions, and likewise each Cu(II) ion connects to three PIA^2? ligands, giving a 3-D framework with utp topology and left-/right-handed helical channels. Interestingly, two such identical frameworks interlock with each other to generate a twofold interpenetrated structure that is stabilized by hydrogen bonding and π–π interactions. In addition, the thermal stability and the magnetic properties of 1 have been investigated.     

Syntheses,crystal structures and luminescent properties of two new Zn(II) coordination polymers based on a dicarboxylate and different imidazole-containing ligands

To investigate the effect of different imidazole-containing ligands on the structure of coordination polymers, two new Zn(II) coordination polymers based on 1,4-cyclohexanedicarboxylic acid (H₂cda) and two different imidazole-containing ligands, [Zn(cda)(bib)_0.5]_n (1) and [Zn(cda)(bmib)_0.5]_n (2) (bib = 1,4-bis(imidazol-1-yl)benzene and bmib = 1,4-bis(2-methylimidazol-3-ium-yl)benzene), have been synthesized and characterized by single-crystal X-ray diffraction. Complex 1 shows a 3-D structure with point symbol (4.8².10³).(4.8²). Complex 2 displays a 2-D layer structure with an –AB– stacking sequence.     

Syntheses and crystal structures of organoindium(III) 1-D coordination polymers with bis(diphenylphosphino)alkane dioxides

Abstract

Bromomethyl-dibromo-indium(III), Br₂InCH₂Br, obtained from indium monobromide and methylene dibromide, reacts with hard and soft donor ligands to afford the corresponding indium(III) organometallic complexes. In this work, we investigated the conditions to prepare adducts of Br₂InCH₂Br using bis(diphenylphosphino)alkane dioxides acting as hard ligands. We report here the synthesis and crystal structures of two 1-D coordination polymers with the hard donor ligands Ph₂P(O)(CH₂)_mP(O)Ph₂ (m = 2, dppeO₂ and m = 6, dpphO₂). Compounds 1 and 2 with formulas [Br₂In(CH₂Br)(dppeO₂)]_n (1) and [Br₂In(CH₂Br)(dpphO₂)]_n (2) were characterized by IR and Raman spectroscopy and elemental analysis. We also obtained an ionic indium(III) compound with dppeO₂ acting as a chelating ligand with formula [InBr₂(dppeO₂)₂][InBr₃(CH₂Br)] (3). The crystal structures were determined for 1–3 using single crystal X-ray diffractometry. The geometry around the In(III) can be described as a trigonal bipyramid in 1 and 2, and the chains were packed onto the plane giving layers that are stabilized mainly by intermolecular interactions. Compound 3 has a square bipyramidal In(III) cation with formula [Br₂L₂In]⁺ and tetrahedral organoindium(III) anion with formula [Br₃InCH₂Br]^–. Hirshfeld surface analysis employing 2-D fingerprint plots have been used to analyze intramolecular and intermolecular interactions present in the solid state of the structures.     

以三(4-咪唑基苯基)胺为配体的镉配合物的合成、晶体结构和荧光性质

以三(4-咪唑基苯基)胺(TIPA)和碘化镉为原料,分别与环已二酸(H_2CDC)和5-甲基间苯二甲酸(H_2MPDA)在水热条件下反应,得到2个结构不同的配位聚合物[CdI(TIPA)(CDC)_(0.5)]_n(1)和{[Cd(TIPA)(MPDA)]·H_2O}_n(2)。对它们进行了元素分析、红外光谱分析,并利用X射线衍射测定了它们的单晶结构。单晶结构分析显示,配合物1拥有二维两重贯穿的(3,4)-连接的(4.5~2)(4.5~3.7~2)拓扑结构,层与层之间通过弱相互作用连接成三维超分子结构;而配合物2具有二维(3,5)-连接的(4~2.6~7.8)(4~2.6)拓扑的层状结构,层与层之间通过互锁方式连接成三维金属有机骨架。结果说明了有机羧酸在配合物组装过程中起着非常重要的作用。此外,在室温下对2个配合物进行了荧光性质分析。     

Syntheses, structures and magnetic properties of a family of one-dimensional M(Ⅱ)-lanthanide(Ⅲ) (M =Ni(Ⅱ) and Zn(Ⅱ)) coordination polymers

A series of 1D nickel(Ⅱ)/zinc(Ⅱ)-lanthanide(Ⅲ) coordination polymers, [M(μ-L)2Ln(NO3)3]n· solvents (HL =bis(2-pyridylcarbonyl)amine; M = Ni, Ln = Gd (1 · NiGd), Tb (2· NiTb), Dy (3· NiDy), Ho (4· NiHo), Y (5· NiY);M = Zn, Ln =Gd (6· ZnGd), Tb (7· ZnTb), Dy (8· ZnDy), Ho (9· ZnHo); solvents = H2O or H2O-ethanol), was synthesized and characterized. All of the complexes are isostructural at 293 K and crystallize in the orthorhombic space group Fddd. Magnetic measurements were performed on 1-9, where weak ferromagnetic interaction is found in 1 · NiGd, ferromagnetic interaction in 2·NiTb and 3·NiDy, and antiferromagnetic interaction in 4· NiHo. A remarkable dc magnetic field dependence of ac susceptibilities was found in this series of complexes.     

Hydrothermal synthesis,crystal structure and photoluminescence of two homochiral zinc(II) coordination polymers

Metal–organic frameworks (MOFs) have potentially useful applications and an intriguing variety of architectures and topologies. Two homochiral coordination polymers have been synthesized by the hydrothermal method, namely poly[(μ‐N‐benzyl‐L‐phenylalaninato‐κ⁴O,O′:O,N)(μ‐formato‐κ²O:O′)zinc(II)], [Zn(C₁₆H₁₆NO₂)(HCOO)]_n, (1), and poly[(μ‐N‐benzyl‐L‐leucinato‐κ⁴O,O′:O,N)(μ‐formato‐κ²O:O′)zinc(II)], [Zn(C₁₃H₁₈NO₂)(HCOO)]_n, (2), and studied by single‐crystal X‐ray diffraction, elemental analyses, IR spectroscopy and fluorescence spectroscopy. Compounds (1) and (2) each have a two‐dimensional layer structure, with the benzyl or isobutyl groups of the ligands directed towards the interlayer interface. Photoluminescence investigations show that both (1) and (2) display a strong emission in the blue region.     

4,4'-二(1-咪唑基)苯硫醚及邻苯二甲酸根构筑的两个配位聚合物的合成、晶体结构及荧光性质

在温和的水热条件下,以4,4'-二(1-咪唑基)苯硫醚(BIDPT)和邻苯二甲酸(H₂pht)为配体,合成了2个配位聚合物{[Zn(BIDPT)(pht)]₂·2H₂O·CH₃OH}_n(1)和{[Cd₅(BIDPT)₄(pht)₅]·H₂O}_n(2),分别用X-射线单晶衍射、元素分析和IR等手段对它们进行了表征。结果表明,配位聚合物1和2为2D层状结构,配位聚合物1属于正交晶系,Pbcn空间群;配位聚合物2属于三斜晶系,P2₁/c空间群。此外还考察了1和2的热稳定性和固体荧光性质。     

Synthesis,crystal structures and magnetic and electrochemiluminescence properties of three manganese(II) complexes

Three novel complexes, namely, penta‐μ‐acetato‐bis(μ₂‐2‐{[2‐(6‐chloropyridin‐2‐yl)hydrazinylidene]methyl}‐6‐methoxyphenolato)‐μ‐formato‐tetramanganese(II), [Mn₄(C₁₃H₁₁ClN₃O₂)₂(C₂H₃O₂)_5.168(CHO₂)_0.832], 1 , hexa‐μ₂‐acetato‐bis(μ₂‐2‐{[2‐(6‐bromopyridin‐2‐yl)hydrazinylidene]methyl}‐6‐methoxyphenolato)tetramanganese(II), [Mn₄(C₁₃H₁₁BrN₃O₂)₂(C₂H₃O₂)₆], 2 , and catena‐poly[[μ₂‐acetato‐acetatoaqua(μ₂‐2‐{[2‐(6‐chloropyridin‐2‐yl)hydrazinylidene]methyl}‐6‐methoxyphenolato)dimanganese(II)]‐μ₂‐acetato], [Mn₂(C₁₃H₁₁ClN₃O₂)(C₂H₃O₂)₃(H₂O)]_n, 3 , have been synthesized using solvothermal methods. Complexes 1 – 3 were characterized by IR spectroscopy, elemental analysis and single‐crystal X‐ray diffraction. Complexes 1 and 2 are tetranuclear manganese clusters, while complex 3 has a one‐dimensional network based on tetranuclear Mn₄(L¹)₂(CH₃COO)₆(H₂O)₂ building units (L¹ is 2‐{[2‐(6‐chloropyridin‐2‐yl)hydrazinylidene]methyl}‐6‐methoxyphenolate). Magnetic studies reveal that complexes 1 – 3 display dominant antiferromagnetic interactions between Mn^II ions through μ₂‐O bridges. In addition, 1 – 3 also display favourable electrochemiluminescence (ECL) properties.