Syntheses and Structures of Coordination Polymers Constructed by Semi‐Rigid Bicarboxylic Acid Ligands

The complexes [Co(L¹)(mpy)] ( 1 ), [Ni(L¹)(mpy)] ( 2 ), [Co(L¹)(tbpy)] · 2H₂O ( 3 ), [Ni₂(L¹)₂(tbpy)₂] · 5H₂O ( 4 ), [Mn₂(L¹)₂(tbpy)₂] · 3H₂O ( 5 ), [Mn(L¹)(biim‐3)] ( 6 ), [Ni₂(L¹)₂(btb)₂(H₂O)] · 2H₂O ( 7 ), [Cu(L²)(mpy)] · 7H₂O ( 8 ), [Co(L²)(tbpy)(H₂O)] ( 9 ), [Ni(L²)(tbpy)(H₂O)] · H₂O ( 10 ), [Cu(L²)(bib)] · 2H₂O ( 11 ), and [Cu(L²)(btb)] · 2H₂O ( 12 ) [H₂L¹ = (3‐carboxyl‐phenyl)‐(4‐(2′‐carboxyl‐phenyl)‐benzyl)ether, H₂L² = 3‐carboxy‐1‐(4′‐carboxybenzyl)‐2‐oxidopyridinium, mpy = 2‐(4‐(4′‐methylphenyl)‐6‐(pyrindin‐2‐yl)pyridin‐2‐yl)pyridine), tbpy = 2‐(4‐(4′‐tert‐butylphenyl)‐6‐(pyrindin‐2‐yl)pyridin‐2‐yl)pyridine), biim‐3 = 1,3‐bis(imidazol‐1′‐yl)propane, btb = 1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene, bib = 1,4‐bis(imidazol‐1′‐ylmethyl)benzene] were synthesized. Compounds 1 – 6 have similar 1D chain structures, which are further linked by π–π interactions to generate supramolecular double chains for 1 and 2 , and supramolecular layers for 3 – 6 . Compound 7 displays a 3D 6‐connected framework with (4⁴ · 6¹¹) topology. Compound 8 features a monomolecular structure, which is further linked by hydrogen bonds between the lattice water molecules and carboxylate oxygen atoms of L² anions to form a 2D supramolecular layer. The monomolecular structures of 9 and 10 are connected by hydrogen bonds and π–π interactions simultaneously to generate supramolecular layers. Compounds 11 and 12 show layer structures.     

catena‐Poly[hexaaquamagnesium(II) [bis(μ3‐5‐nitro‐2‐oxidoisophthalato)dicopper(II)] dihydrate]

In the centrosymmetric dinuclear anions of the title bimetallic complex, {[Mg(H₂O)₆][Cu₂(C₈H₂NO₇)₂]·2H₂O}_n, each Cu^II ion is strongly coordinated by four O atoms in a distorted square‐planar geometry. Two of these O atoms belong to phenolate groups and the other two to carboxylate groups from 5‐nitro‐2‐oxidoisophthalate (L1) trianions, derived from 5‐nitrobenzene‐1,2,3‐tricarboxylic acid (O₂N–H₃L). The phenolate O atoms bridge the two Cu^II ions in the anion. In addition, each Cu^II cation interacts weakly with a symmetry‐related carboxylate O atom of an adjacent L1 ligand, giving a square‐pyramidal coordination geometry. The copper residue forms a ladder‐like linear coordination polymer via L1 ligands. The [Mg(H₂O)₆]²⁺ cations sit on centres of inversion. The polymeric anions, cations and free water molecules are self‐assembled into a three‐dimensional supramolecular network via O—H...O hydrogen bonds.     

Syntheses,Characterization, and Electrochemical Lithium‐Ion Storage Properties of Two Cobalt(II) Coordination Polymers Containing 5‐Hydroxyisophthalic Acid and Bis‐benzoimidazole Ligands

Two cobalt(II) coordination polymers, namely {[Co(HO‐BDC)(bbe)] · (H₂O)}_n ( 1 ), and {[Co(O‐BDC)(bbp)] · (H₂O)}_n ( 2 ) (HO‐H₂BDC = 5‐hydroxyisophthalic acid, bbe = 1, 2‐bis(benzoimidazol‐2‐yl)ethane, and bbp = 1, 3‐bis(benzoimidazol‐2‐yl)propane) were synthesized under hydrothermal conditions, and characterized by elemental analyses, IR spectroscopy, single‐crystal X‐ray diffraction, and thermogravimetric analyses. Compound 1 is a 1D chain, whereas 2 is a (3, 3)‐connected 2D network with (6³) topology. These two 1D and 2D complexes are further connected by hydrogen bonds to form the 3D supramolecular architectures. The electrochemical lithium‐ion storage properties of the as‐made Co₃O₄ by calcination of 1 are investigated in detail.     

Two coordination polymers constructed by 5‐[(4‐carboxyphenoxy)methyl]benzene‐1,3‐dicarboxylic acid and 2,2′‐bipyridine: syntheses,structures and luminescence properties

Coordination polymers (CPs) have attracted increasing interest in recent years. In this work, two new CPs, namely poly[[aquabis(2,2′‐bipyridine‐κ²N,N′){μ₃‐5‐[(4‐carboxylatophenoxy)methyl]benzene‐1,3‐dicarboxylato‐κ⁴O¹,O^1′:O³:O⁵}(μ‐formato‐κ³O:O,O′)dicadmium(II)] monohydrate], {[Cd₂(C₁₆H₉O₇)(HCO₂)(C₁₀H₈N₂)₂(H₂O)]·H₂O}_n ( 1 ), and poly[[(2,2′‐bipyridine‐κ²N,N′){μ₃‐5‐[(4‐carboxylphenoxy)methyl]benzene‐1,3‐dicarboxylato‐κ⁴O¹,O^1′:O³:O⁵}manganese(II)] sesquihydrate], {[Mn(C₁₆H₁₀O₇)(C₁₀H₈N₂)]·1.5H₂O}_n ( 2 ), have been prepared using the tricarboxylic acid 5‐[(4‐carboxyphenoxy)methyl]benzene‐1,3‐dicarboxylic acid and 2,2′‐bipyridine under hydrothermal conditions. CP 1 displays a two‐dimensional layer structure which is further extended into a three‐dimensional (3D) supramolecular structure via intermolecular π–π interactions, while CP 2 shows a different 3D supramolecular structure extended from one‐dimensional ladder chains by intermolecular π–π interactions. In addition, the solid‐state luminescence spectra of 1 and 2 were studied at room temperature.     

Synthesis,Crystal Structures,and Thermal Analyses of ­Copper(II) and Manganese(II) Mixed‐Ligand Coordination Polymers Constructed from Benzimidazole‐5, 6‐dicarboxylic Acid and N‐Donor Ligands

The coordination polymers, {[Cu(Hbidc)(2, 2′‐bpy)(H₂O)] · 2H₂O}_n ( 1 ) and {[Mn(Hbidc)(2, 2′‐bpy) (H₂O)₂] · 2H₂O}_n ( 2 ) (H₃bidc = benzimidazole‐5, 6‐dicarboxylic acid, 2, 2′‐bpy = 2, 2′‐bipyridine), were synthesized in solution and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), and single‐crystal X‐ray diffraction. Complexes 1 and 2 consist of different 1D chain structures. In both compounds, 2, 2′‐bpy is chelating in a bidentate manner, whereas the Hbidc ligands in complexes 1 and 2 display chelating‐bridging tridentate and bridging bidentate coordination modes. The two complexes are further extended into 3D supramolecular structures through O–H ··· O and N–H ··· O hydrogen bonds. The thermal stabilities of complexes 1 and 2 were studied by thermogravimetric analyses (TGA).     

基于一种柔性和角型有机芳香多酸配体的两种3D配位聚合物的合成、结构和荧光性

通过水热合成的方法制得具有三维超分子结构的2种配位聚合物{[Zn（L）（bpa）_0.5（H₂O）₂]·2.25H₂O}_n （1）和{[Cd（L）（H₂O）]·2H₂O}_n （2）,其中,H₃LCl为氯化5-（4-羟基吡啶基甲基）间苯二甲酸,bpa为1,2-二（4-吡啶基）乙烷。这2种化合物的结构通过单晶X射线衍射、红外光谱（IR）、元素分析、热重分析（TG）等方法进行了表征。结构解析表明：化合物1是一种梯型链式结构,并通过链间氢键作用延伸成了3D超分子网络;化合物2为含有大量一维隧道空腔的2D配位网络。此外,研究了这2种化合物的荧光性质。     

catena‐Poly[[[(benzene‐1,3,5‐tricarboxylic acid)(1,10‐phenanthroline)cadmium(II)]‐μ‐oxalato] 1H‐benzotriazole solvate monohydrate]

In the title compound, [Cd(C₂O₄)(C₁₂H₈N₂)(C₉H₆O₆)]·C₆H₅N₃·H₂O, the Cd^II atom has a distorted pentagonal–bipyramidal geometry, defined by two N atoms and five O atoms from bidentate 1,10‐phenanthroline ligands, oxalate ligands and benzene‐1,3,5‐tricarboxylic acid ligands. The oxalate ligands in the asymmetric unit possess inversion symmetry. The triazole molecule is not coordinated to the Cd atom. The structure of the title compound features a one‐dimensional chain running along the crystallographic a axis, and a three‐dimensional supramolecular network is formed via aromatic π–π interactions and hydrogen‐bonding interactions.     

Mixed‐ligand Complexes with 2,6‐Pyridinedicarboxylato(2‐) and 4,7‐Diphenyl‐1,10‐Phenanthroline Ligands, [MII(pdc)(DPphen)(H2O)]·H2O (M = Co or Cu). Synthesis,Crystal Structures and Properties

Iso‐type [M^II(pdc)(DPphen)(H₂O]·H₂O compounds (M = Co or Cu, pdc = 2,6‐pyridinedicarboxylato(2‐) ligand and DPphen = 4,7‐diphenyl‐1,10‐Phenanthroline) were synthesized and studied by X‐ray diffraction, thermal and spectral methods. The N,N′‐equatorial bidentate DPphen‐copper(II) chelation imposes a mer‐N(equatorial)+O₂(apical) conformation to pdc in the coordination polyhedron (type 4+1+1). In the Co(II) derivative, the coordination is of type 1+2+2+1 because of a lesser Jahn‐Teller distortion. In the crystals, π,π‐interligand interactions between phen ligands connect the complex molecules in multi‐stacked chains. Aqua···O(carboxyl) H‐bonding interactions reinforce the stacked chains and build double chains in 1D supramolecular structures parallel to the a axis. Non coordinated water connect these structures by H‐bonds.     

Influence of Flexible Bis(benzimidazole) Derivatives on the Self‐assembly of Three Mixed Ligands Silver(I) Coordination Polymers

Three silver(I) coordination polymers namely, [Ag₄(L1)₂(1, 4‐ndc)₂]_n ( 1 ) {[Ag(L2)] · (1, 4‐Hndc) · H₂O}_n ( 2 ), and {[Ag(L3)(H₂O)] · (1, 4‐Hndc)}_n ( 3 ) [L1 = 1, 3‐bis(benzimidazol‐1‐ylmethyl)benzene, 1, 4‐H₂ndc = 1, 4‐naphthalenedicarboxylic acid, L2 = 1, 3‐bis(5, 6‐dimethylbenzimidazole‐1‐ylmethyl)benzene, L3 = 1, 4‐bis(5, 6‐dimethylbenzimidazole)butane], were hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction analysis, elemental analysis, IR spectroscopy, thermogravimetric and XRPD analysis. Complex 1 displays a 1D tube‐like chain, which is packed into a 3D supramolecular network by π–π stacking interactions. Complex 2 features an infinite 1D linear chain. Complex 3 contains a 1D wave‐like chain, which is extended into a 3D supramolecular network through O–H ··· O hydrogen bonding interactions. Moreover, these coordination polymers exhibit catalytic properties for degradation of methyl orange in Fenton‐like processes.     

Complexes of nickel(II) and copper(II) with 1,2,4‐triazole‐3‐carboxylic acid and of cobalt(III) with 3‐amino‐1,2,4‐triazole‐5‐carboxylic acid

Because of their versatile coordination modes and strong coordination ability for metals, triazole ligands can provide a wide range of possibilities for the construction of metal–organic frameworks. Three transition‐metal complexes, namely bis(μ‐1,2,4‐triazol‐4‐ide‐3‐carboxylato)‐κ³N ²,O :N ¹;κ³N ¹:N ²,O‐bis[triamminenickel(II)] tetrahydrate, [Ni₂(C₃HN₃O₂)₂(NH₃)₆]·4H₂O, (I), catena‐poly[[[diamminediaquacopper(II)]‐μ‐1,2,4‐triazol‐4‐ide‐3‐carboxylato‐κ³N ¹:N ⁴,O‐[diamminecopper(II)]‐μ‐1,2,4‐triazol‐4‐ide‐3‐carboxylato‐κ³N ⁴,O :N ¹] dihydrate], {[Cu₂(C₃HN₃O₂)₂(NH₃)₄(H₂O)₂]·2H₂O}_n , (II), (μ‐5‐amino‐1,2,4‐triazol‐1‐ide‐3‐carboxylato‐κ²N ¹:N ²)di‐μ‐hydroxido‐κ⁴O :O‐bis[triamminecobalt(III)] nitrate hydroxide trihydrate, [Co₂(C₃H₂N₄O₂)(OH)₂(NH₃)₆](NO₃)(OH)·3H₂O, (III), with different structural forms have been prepared by the reaction of transition metal salts, i.e. NiCl₂, CuCl₂ and Co(NO₃)₂, with 1,2,4‐triazole‐3‐carboxylic acid or 3‐amino‐1,2,4‐triazole‐5‐carboxylic acid hemihydrate in aqueous ammonia at room temperature. Compound (I) is a dinuclear complex. Extensive O—H…O, O—H…N and N—H…O hydrogen bonds and π–π stacking interactions between the centroids of the triazole rings contribute to the formation of the three‐dimensional supramolecular structure. Compound (II) exhibits a one‐dimensional chain structure, with O—H…O hydrogen bonds and weak O—H…N, N—H…O and C—H…O hydrogen bonds linking anions and lattice water molecules into the three‐dimensional supramolecular structure. Compared with compound (I), compound (III) is a structurally different dinuclear complex. Extensive N—H…O, N—H…N, O—H…N and O—H…O hydrogen bonding occurs in the structure, leading to the formation of the three‐dimensional supramolecular structure.     

Co‐crystallization of hemimellitic acid with 4,4′‐bipyridine forming a pillar‐layered hydrogen‐bonded network

Co‐crystallization of hemimellitic acid (benzene‐1,2,3‐tricarboxylic acid) dihydrate (H₃HMA·2H₂O) with 4,4′‐bipyridine (4,4′‐bpy) affords the 1:1 co‐crystal benzene‐1,2,3‐tricarboxylic acid–4,4′‐bipyridine (1/1), H₃HMA·4,4′‐bpy or C₉H₆O₆·C₁₀H₈N₂. Strong O—H⋯O hydrogen bonds connect the acid mol­ecules to form a one‐dimensional zigzag chain, around which the 4,4′‐bpy components are fixed as arms via O—H⋯N inter­actions, resulting in a ladder motif. Through weak C—H⋯O non‐covalent forces, the resulting acid layers are extended into a three‐dimensional pillar‐layered architecture supported by rod‐like 4,4′‐bpy components. The influence on hydrogen‐bonding models is also discussed, with the discovery of an unexpected inter­action motif that does not follow the routine hydrogen‐bonded hierarchical rule in the construction of an acid–base co‐crystal.     

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.     

Co(en)3[B4O5(OH)4]Cl·3H2O和[Ni(en)3][B5O6(OH)4]2·2H2O的合成、结构以及热力学性质

利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。     

A new copper(II) supramolecular coordination polymer and a dinuclear compound with multifunctional 2‐amino‐5‐sulfobenzoic acid and flexible N‐donor ligands: synthesis,structure and characterization

Multifunctional 2‐amino‐5‐sulfobenzoic acid (H₂afsb) can exhibit a variety of roles during the construction of supramolecular coordination polymers. The pendant carboxylic acid, sulfonic acid and amino groups could not only play a role in directing bonding but could also have the potential to act as hydrogen‐bond donors and acceptors, resulting in extended high‐dimensional supramolecular networks. Two new Cu^II coordination compounds, namely catena‐poly[[[diaquacopper(II)]‐μ‐1,6‐bis(1H‐1,2,4‐triazol‐1‐yl)hexane‐κ²N⁴:N^4′] bis(3‐amino‐4‐carboxybenzenesulfonate) dihydrate], {[Cu(C₁₀H₁₆N₆)₂(H₂O)₂](C₇H₆NO₅S)₂·2H₂O}_n or {[Cu(bth)₂(H₂O)₂](Hafsb)₂·2H₂O}_n, (1), and bis(μ‐2‐amino‐5‐sulfonatobenzoato‐κ²O¹:O^1′)bis{μ‐1,2‐bis[(1H‐imidazol‐1‐yl)methyl]benzene‐κ²N³:N^3′}bis[aquacopper(II)] trihydrate, [Cu₂(C₇H₅NO₅S)₂(C₁₄H₁₄N₄)₂(H₂O)₂]·3H₂O or [Cu₂(afsb)₂(obix)₂(H₂O)₂]·3H₂O, (2), have been obtained through the assembly between H₂afsb and the Cu^II ion in the presence of the flexible N‐donor ligands 1,6‐bis(1H‐1,2,4‐triazol‐1‐yl)hexane (bth) and 1,2‐bis[(1H‐1,2,4‐triazol‐1‐yl)methyl]benzene (obix), respectively. Compound (1) consists of a cationic coordination polymeric chain and 3‐amino‐4‐carboxybenzenesulfonate (Hafsb⁻) anions. Compound (2) exhibits an asymmetric dinuclear structure. There are hydrogen‐bonded networks within the lattices of (1) and (2). Interestingly, both (1) and (2) exhibit reversible dehydration–rehydration behaviour.     

Syntheses,Structures, and Luminescent Properties of d10 Coordination Polymers with 2‐(4‐Carboxyphenyl)‐imidazo[4, 5‐f]‐1, 10‐phenanthroline and 1, 3‐Benzenedicarboxylate Derivatives

Four Zn^II/Cd^II coordination polymers (CPs) based on 2‐(4‐carboxy‐phenyl)imidazo[4, 5‐f]‐1, 10‐phenanthroline (HNCP) and different derivatives of 5‐R‐1, 3‐benzenedicarboxylate (5‐R‐1, 3‐BDC) (R = NO₂, H, OH), [Zn(HNCP)(5‐NO₂‐1, 3‐BDC)]_n ( 1 ), [Cd(HNCP)(5‐NO₂‐1, 3‐BDC)]_n ( 2 ), [Zn(HNCP)(1, 3‐BDC)(H₂O)₂]_n ( 3 ), and {[Zn(HNCP)(5‐OH‐1, 3‐BDC)(H₂O) · H₂O}_n ( 4 ) were synthesized under hydrothermal conditions. Compounds 1 – 4 were determined by elemental analyses, IR spectroscopy, and single‐crystal and powder X‐ray diffraction. Compounds 1 and 2 are isomorphous, presenting a 4‐connected uninodal (4, 4)‐sql 2D framework with threefold interpenetration, which are further extended into the three‐dimensional (3D) supramolecular architecture through π ··· π stacking interactions between the aryl rings of 5‐NO₂‐1, 3‐BDC. Compared to compound 1 , 3 is obtained by using different reaction temperatures and metal‐ligand ratios, generating a 3D framework with –ABAB– fashion via π ··· π stacking interactions. Compound 4 is a 1D chain, which is further extended into a 3D supramolecular net by hydrogen bonds and π ··· π stacking interactions. The thermogravimetric and fluorescence properties of 1 – 4 were also explored.     

Synthesis,Structure, Magnetic Properties,and Catalase‐like Activity of Methoxy‐bridged Manganese(III) Coordination Polymer containing Hydrazone based (O,N,O)2‐Donor Ligand

A 1D coordination polymer of manganese(III) with a hydrazone‐based ligand, [Mn₂(L)(μ‐OCH₃)₂(OHCH₃)₂]_n ( 1 ), was synthesized and characterized by elemental analyses and spectroscopic methods {H₄L = bis[(2‐hydroxynaphthalen‐1‐yl)methylene]adipohydrazide}. The crystal structure of 1 was determined by X‐ray crystallography. The two dianionic domains of the ligand adopt trans configuration, and each coordinates in a tridentate mode via the O, N, O′‐donor atoms to a Mn^III ion forming a dinuclear compound. The methoxy ligands provide an asymmetric bridge between two central manganese atoms, which lead to the formation of a 1D coordination polymer. A 2D supramolecular structure is formed by hydrogen bonding interactions between the 1D chains. Although the methoxy ligands are labile, the polymer preserves its oligonuclearity in the solution. Temperature‐dependent magnetic susceptibility studies proved the presence of a weak antiferromagnetic interaction between manganese(III) ions with J = –3.2 cm^–1, which results from axial distortion of the manganese coordination environment. Compound 1 showed catalase‐like activity in disproportionation of H₂O₂.     

Four New Compounds Based on Terephthalate and 2‐(4‐Pyridyl)benzimidazole Ligands

Four new compounds based on H₂BDC and PyBIm [H₂BDC = 1,4‐benzenedicarboxylatic acid, PyBIm = 2‐(4‐pyridyl)benzimidazole], (PyBIm)(H₂BDC)_0.5 ( 1 ), Co(PyBIm)₂(HBDC)(BDC)_0.5 ( 2 ), Ni(PyBIm)₂(HBDC)(BDC)_0.5 ( 3 ), and Zn(BDC)(PyBIm) · H₂O ( 4 ), were synthesized by hydrothermal methods and characterized by X‐ray diffraction. Compound 1 contains two types of hydrogen bonding N–H ··· N and O–H ··· N, which connect the molecules into a two‐dimensional (2D) layer. Complex 2 crystallizes isostructural to 3 in triclinic space group P$\bar{1}$ , in 1D chains. The hydrogen‐bonding interactions between uncoordinated N, N–H and COOH groups in 2 connect the 1D chains into a 2D layer. Complex 4 displays a 1D structure, which is finally extended to a 3D supramolecular framework by hydrogen bonding and π–π packing interactions. The magnetic properties of compounds 2 and 3 were studied as well.     

Supramolecular Architectures with Open Frameworks Constructed by Transitional Metal Ions,Linear Dicarboxylic Acid,and 2,2′‐Bipyridine

Four new transitional metal supramolecular architectures, [Zn(cca)(2,2′‐bpy)]_n · n(2,2′‐bpy) ( 1 ), [Cu(cca)(2,2′‐bpy)]_n ( 2 ), [Zn(bpdc)(2,2′‐bpy)(H₂O)]_n · 0.5nDMF · 1.5nH₂O ( 3 ), and [Co(bpdc)(2,2′‐bpy)(H₂O)]_n · nH₂O ( 4 ) (H₂cca = p‐carboxycinnamic acid; H₂bpdc = 4,4′‐biphenyldicarboxylic acid; 2,2′‐bpy = 2,2′‐bipyridine) were synthesized by hydrothermal reactions and characterized by single crystal X‐ray diffraction, elemental analyses, and IR spectroscopy. Although the metal ions in these four compounds are bridged by linear dicarboxylic acid into 1D infinite chains, there are different π–π stacking interactions between the chains, which results in the formation of different 3D supramolecular networks. Compound 1 is of a 3D open‐framework with free 2,2′‐bpy molecules in the channels, whereas compound 2 is of a complicated 3D supramolecular network. Compounds 3 and 4 are isostructural. Both compounds have open‐frameworks.     

Syntheses,Structures, and Luminescent Properties of Two Cadmium(II) Coordination Compounds based on a Sulfonate Functionalized Terpyridine Ligand

The coordination compounds [Cd(TBDS)(H₂O)₂]_n ( 1 ) and Cd(TBDS)(bpy)₂(H₂O) · 3H₂O ( 2 ) {H₂TBDS = 4‐([4,2′:6′,4′′‐terpyridine]‐4′‐yl)benzene‐1,3‐disulfonic acid, bpy = 2,2′‐bipyridine} were synthesized under hydrothermal conditions. Single crystal X‐ray diffraction analyses revealed that compound 1 is a twofold interpenetrating 3D framework with 4‐connected dia topology, whereas compound 2 is a mononuclear compound, which packed with each other via hydrogen‐bonding interactions to construct a three‐dimensional supramolecular structure, and contained unusual meso‐helical chains. Additionally, the luminescence properties and thermal stabilities of 1 and 2 were investigated.     

Three Silver(I) Coordination Polymers Constructed from Flexible Bis(benzimidazole) and Carboxylates Ligands

Under hydrothermal conditions, three new Ag^I coordination polymers, [Ag(L1)(Hmip)]_n ( 1 ), [Ag(L2)_0.5(ndc)_0.5]_n ( 2 ), and {[Ag(L3)_0.5(Htbi)] · 0.25H₂O}_n ( 3 ) [H₂mip = 5‐methylisophthalic acid, L1 = 1,4‐bis(2‐methylbenzimidazol‐1‐ylmethyl)benzene, H₂ndc = 2,6‐naphthalenedicarboxylic acid, L2 = 1,3‐bis(2‐methylbenzimidazol‐1‐ylmethyl)benzene, H₂tbi = 5‐tert‐butyl isophthalic acid, L3 = 1,4‐bis(5,6‐dimethylbenzimidazole)butane] were synthesized by employing flexible bis(benzimidazole) and dicarboxylic acid ligands. Polymer 1 displays a 2D 4‐connected 4L2 underlying net topology with the point symbol of (6⁵.8) in standard representation. Compound 2 possesses a 2D uninodal 4‐connected Shubnikov tetragonal plane net (sql) based on a dinuclear Ag^I clusters with the point symbol (4⁴.6²), which is further extended into a 3D supramolecular framework by π–π interactions. Compound 3 possesses dinuclear molecular complex groups, which form chains by weak Ag–O (2.6 Å) coordination bonds, and further assembled into a 2D supramolecular layer by hydrogen bonds and π–π stacking interactions. These complexes exhibit intense fluorescent emissions in solid state. UV/Vis diffuse reflection spectra and the excellent catalytic activity for the degradation of the congo red azo dye in a Fenton‐like process are discussed.