Synthesis and Structures of Infinite Coordination Polymers from 1,3‐Bis(4‐pyridyl)propane Ligand and Zinc Salts

The reaction of Zn(NO₃)₂‐6H₂O, NH₄SCN and bpp (bpp = 1,3‐bis(4‐pyridyl)propane) in CH₃OH afforded the complex [Zn(NCS)₂(bpp)]_n, 1 , while the reaction of Zn(ClO₄)₂‐6H₂O and bpp in CH₃OH afforded the complex [Zn(ClO₄)₂(bpp)₂]_n, 2 . Both complexes have been characterized by spectroscopic methods and their structures have been determined by X‐ray crystallography. Crystal data for 1 : Orthorhombic, space group P2₁2₁2, a= 12.857(6), b = 14.822(7), c = 4.820(2) Å, β = 90°, V = 918.5(8) ų, Z = 2 with final residuals R1 = 0.0747 and wR2 = 0.1657. Crystal data for 2 : Tetragonal, space group I4/mcm, a = 11.612(1), b = 11.612(1), c = 23.247(9) Å, β = 90°, V = 3135(1) ų, Z = 4 with final residuals R1 = 0.0523 and wR2 = 0.1064. The coordination polymers display a variety of structural architectures, ranging from zigzag chains ( 1 ) and one‐dimensional channel‐type architectures ( 2 ). The effects of the orientation of the nitrogen atom in the pyridine rings on the resultant structures are discussed.     

Synthesis and Luminescent Properties of Two Zinc(II) Coordination Polymers Constructed by 4‐(Pyridin‐4‐ylmethoxy)benzolic Acid Ligand

Two coordination polymers, namely [Zn(L)Cl] ( 1 ) and [Zn(L)₂] ( 2 ) [L = 4‐(pyridin‐4‐ylmethoxy)benzolic acid] were synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction analyses, powder X‐ray diffraction, and thermogravimetric analysis. Compounds 1 and 2 have a two‐dimensional square‐shaped structure (the dimensions are 15.43 × 15.43 Å for 1 and 12.064 × 15.017 Å for 2 ) with (4⁴ · 6²) topology. Moreover, compounds 1 and 2 exhibit a 3D supramolecular structure made up by strong π–π interactions from the adjacent layers. Furthermore, compounds 1 and 2 show good fluorescence properties in the solid state at room temperature.     

Two‐Dimensional and Three‐Dimensional Lanthanide Coordination Polymers Built from 4‐Hydroxypyridine‐2,6‐dicarboxylic Acid Ligand

4‐Hydroxypyridine‐2,6‐dicarboxylic acid (H₃CAM) reacts with Ln₂O₃(Ln = La, Ce) or Ln(NO₃)₃ (Ln = Sm, Dy, Gd, Ho) in hydrothermal reactions to form a series of lanthanide coordination polymers 1 – 6 . Elemental analysis, IR spectra and X‐ray crystal structure analysis were carried out to determine the composition and crystal structure of 1 – 6 . Compounds 1 and 2 are isostructural and contain tetranuclear metallic ring unit and 3D framework. 4 – 6 are isostructural contain 2D network. Furthermore, the photoluminescent properties of 3 and 4 at room temperature were also studied.     

Syntheses,Crystal Structures,and Photoluminescence of Zinc(II) and Cobalt(II) Coordination Polymers Based on Semiflexible 1,4‐Bis(4‐phenoxy)benzenedicarboxylate

Hydrothermal reactions of Co(NO₃)₂ · 6H₂O and Zn(NO₃)₂ · 6H₂O with 1,4‐bis(4‐phenoxy)benzenedicarboxylic acid (H₂bcpb) resulted in the formation of the coordination polymers [Zn(bcpb)(Py)]_n ( 1 ), and [Co(bcpb)(Py)₂]_n ( 2 ), respectively. Their structures were studied by single‐crystal and powder X‐ray diffraction methods and further characterized by IR spectroscopy, elemental analyses, and thermogravimetric analyses (TGA). Single X‐ray diffraction analyses revealed that complex 1 has a 1D loop chain. Each repeated unit contains two carboxylate ligands and two SBUs (secondary building units), whereas complex 2 has a 2D 4‐connected sql sheet with point symbol (4⁴.6²). The complexes are further expanded to 3D supramolecular structures through non‐covalent bonding interactions. Besides, photoluminescent property of complex 1 was also investigated in the solid state at room temperature.     

Two Zinc(II) Coordination Polymers Based on the Ligand 1, 4‐Bis[(2‐methyl‐imidazol‐1‐yl)methyl]benzene: Syntheses,Crystal Structures and Properties

Two coordination polymers (CPs), {[Zn₂(BMB)(5‐AIPA)₂] · 2H₂O}_n( 1 ) and [Zn(BMB)(5‐NIPA)]_n( 2 ) {BMB = 1, 4‐bis[(2‐methyl‐imidazol‐1‐yl)methyl]benzene, 5‐AIPA = 5‐aminoisophthalic acid, 5‐NIPA = 5‐nitroisophthalic acid}, were synthesized under hydrothermal conditions. Compound 1 displays a 2D double‐layer structure, which is packed into a 3D supramolecule by interlayer hydrogen bonds and π–π stacking interactions. Compound 2 displays a threefold interpenetrating 3D network, which is composed of left‐handed helical chains and two types of meso‐helical chains along different directions.     

Synthesis,Characterization, and Luminescence of Two New Zinc(II) Coordination Polymers Constructed by 5‐(4‐Carboxybenzyloxy)Isophthalic Acid Ligand

Two coordination polymers, namely Zn(HL)(4,4′‐bpy)_1.5 ( 1 ), [Zn₃(L)₂(BIMB)₂] · 5H₂O ( 2 ) [H₃L = 5‐(4‐carboxybenzyloxy)isophthalic acid, 4,4′‐bpy = 4,4′‐bipyridine, BIMB = 1,4‐bis(1H‐imidazol‐1‐yl)benzene] were synthesized under hydrothermal conditions. Their structures are determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses, IR spectroscopy, and thermogravimetric (TG) analyses. Complex 1 features a 2D 4‐connected network. Complex 2 is a 3D twofold interpenetrating (3,4,6)‐connected net. In addition, the luminescent properties for 1 and 2 were studied in the solid state at room temperature.     

Two Coordination Polymers based on 2‐Ethyl‐1H‐imidazole‐4,5‐dicarboxylic Acid and 1,3‐Bis(4‐pyridyl)propane: Synthesis,Crystal Structures,and Photoluminescent Properties

Two coordination polymers, [Cd(Heidc)(bpp)]_n ( 1 ) and [Zn₃ (eidc)₂(bpp)(H₂O)₂] · 2H₂O}_n ( 2 ) (H₃eidc = 2‐ethyl‐4,5‐imidazole dicarboxylic acid, bpp = 1,3‐bis(4‐pyridyl)propane) were hydrothermally synthesized and characterized by elemental analysis, IR, spectroscopy single‐crystal X‐ray diffraction, and thermogravimetric analyses. Compound 1 features a 2D layer formed by C–H ··· π stacking interactions between adjacent chains, whereas compound 2 shows a 3D (8³)₂(8⁵.10)‐tfc framework constructed of the 2D (6,3) layer. The result demonstrates that the central metal atoms play a key role in governing the coordination motifs. Moreover, solid‐state properties such as thermal stabilities and photoluminescence of 1 and 2 were also investigated.     

Synthesis of a One‐dimensional Coordination Polymer Based on Copper(II) Nitrate and 1,2‐Bis(5‐monomethylhydrazinyl‐1H‐tetrazolyl)ethane

A one‐dimensional coordination polymer based on copper(II) nitrate and 1,2‐bis(5‐monomethylhydrazinyl‐1H‐tetrazolyl)ethane as ligand was prepared. The thermal and physical stability was determined by differential scanning calorimetry and BAM methods. The polymer was investigated by vibrational spectroscopy and single X‐ray diffraction. Moreover, the ligand itself and the 1,2‐bis(1H‐tetrazolyl)ethane were characterized as energetic material by bomb calorimetric measurements along with calculations using the EXPLO5 software. Both compounds have moderate energetic properties along with a high thermal and physical stability. These findings render these compounds into promising environment friendly gas generating agents.     

Syntheses,Structures, and Magnetic Properties of Two Novel Cobalt(II) Coordination Polymers Constructed from Pyridine‐2,6‐dicarboxylic Acid N‐oxide (PDCO)

Two new cobalt(II) coordination polymers, [Co(PDCO)(H₂O)₂]_n ( 1 ) and [Co(PDCO)(bix)(2H₂O)₂·H₂O]_n ( 2 ) ( PDCO= pyridine‐2,6‐dicarboxylic acid N‐oxide, bix = 1,4‐bis(imidazol‐1‐ylmethyl)‐benzene) have been synthesized under hydrothermal conditions. Single‐crystal X‐ray analyses show that compound 1 is a 1D helical chainlike structure with 4₁ screw axes parallel to the crystallographic c‐axis and interchain hydrogen‐bonding interactions further result in a 3D framework; for compound 2 , each bix ligand connects two Co1 atoms (or two Co2 atoms) to give a zigzag chain structure and these 1D chains are connected by offset face‐to‐face π···π and hydrogen bond interactions to generate a 3D architecture. The thermogravimetric analyses were investigated for 1 and 2 . The determination of variable temperature magnetic susceptibilities indicates an antiferromagnetic interaction between the metal atoms for 1 and 2 .     

Solvothermal Synthesis of New Luminescent Zinc(II) Coordination Polymers with One‐Dimensional Homochiral Structures

By using a dual‐ligand approach, two new homochiral zinc(II) coordination polymers, Zn₂(phen)₂(H₂O)₂(cam)₂ · ethanol ( 1 ) and Zn(bipy)(cam) ( 2 ) [phen = 1,10‐phenanthroline, bipy = 2,2′‐bipyridine, H₂cam = (1R,3S)‐(+)‐camphoric acid] have been synthesized under solvothermal conditions. Compound 1 has a zigzag chain‐like structure and compound 2 has a linear chain‐like structure. The two compounds exhibit intense photoluminescence upon photoexcitation at 280 and 290 nm, respectively.     

Crystallographic report: [(1,3‐Bis(4‐pyridyl)propane)(diaqua)zinc(II)] diperchlorate dihydrate

Four ligands of 1,3‐bis(4‐pyridyl)propane and two water molecules are coordinated to the zinc(II) atom so that the coordination geometry closely resembles a trans‐N₄O₂ octahedral environment. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthesis,Crystal Structure,Spectroscopic, Electrochemical and Antimicrobial Properties of Cu(II) Complex with the Mixed Ligands of 2,9‐Dimethyl‐1,10‐phenanthroline and 4‐Hydroxypyridine‐2,6‐dicarboxylic Acid

A mononuclear Cu(II) complex with mixed ligands, formulated as [Cu(hypydc)(dmp)]·H₂O (hypydc=4‐hydroxypyridine‐2,6‐dicarboxylate, dmp=2,9‐dimethyl‐1,10‐phenanthroline), was synthesized and well characterized by single crystal X‐ray diffraction analysis, as well as spectroscopic (IR, UV‐Vis), and electrochemical methods. The Cu(II) atom exhibits a distorted square‐pyramidal geometry. Intermolecular O? H···O and C? H···O hydrogen bonds, π‐π stacking interactions and C? H···π interactions seem to be effective in the stabilization of the crystal structure. The complex was also evaluated for its antimicrobial activity using in vitro microdilution methods. Six standard bacteria and a strain of Candida albicans were used for the antimicrobial activities. There was a very strong activity against Candida albicans and significant activities against Enterococcus fecalis, Listeria monocytogenes, Bacillus cereus and Staphylococcus aureus, indicating important biological activities of the complex.     

Metal Ion‐tuned Complexes based on Benzene‐1, 2, 4, 5‐tetracarboxylic Acid and the Semirigid Ligand 1, 4‐Bis(2‐methylbenzimidazol‐1‐ylmethyl) Benzene

Abstract. Two metal‐organic coordination polymers [Co(bmb)(btc)_0.5]_n( 1 ) and {[Zn(bmb)_0.5(btc)_0.5(H₂O)] · 0.5bmb · H₂O}_n ( 2 ) [H₄btc = benzene‐1, 2, 4, 5‐tetracarboxylic acid, bmb = 1, 4‐bis(2‐methylbenzimidazol‐1‐ylmethyl) benzene] were prepared under hydrothermal conditions. Single‐crystal X‐ray diffraction indicates that both complexes have a 2D framework structure with (4 · 6²) (4² · 6² · 8²) topology. Interestingly, the hydrogen bonds in 2 form a fascinating meso‐helix. The catalytic activity of 1 for oxidative coupling of 2, 6‐dimethylphenol (DMP) and the photoluminescence properties of 2 were investigated. Furthermore, the complexes were investigated by IR spectroscopy and thermogravimetric analysis.     

Three Cadmium(II) Coordination Polymers based on Mixed 1,2‐Naphthalenedicarboxylate and Bis(pyridyl) Co‐ligands: Structural Diversities and Photoluminescent Properties

Hydrothermal reactions of Cd(OAc)₂ · 2H₂O with 1,2‐naphthalic anhydride in the absence/presence of different rigid/flexible bis(pyridyl) co‐ligands, produce three distinct coordination polymers, namely [Cd(ndc)]_n ( 1 ), {[Cd₅(ndc)₄(bpp)₂(OH)₂](H₂O)₄}_n ( 2 ), and [Cd₅(ndc)₄(bpy)₂(OH)₂]_n ( 3 ) [ndc = 1,2‐naphthalenedicarboxylate, bpp = 1,3‐bis(4‐pyridyl)propane, and bpy = 4,4′‐bipyridine]. Complex 1 contains dinuclear [Cd₂O₂] clusters as secondary building units (SBUs) and shows a two‐dimensional (2D) kgd network. Complexes 2 and 3 possess one‐dimensional (1D) chains based on pentanuclear [Cd₅(μ₃‐OH)₂(COO)₂] units as SBUs, which are further extended to afford 2D sql sheet via flexible bpp in 2 and three‐dimensional (3D) pcu network via rigid bpy in 3 , respectively. The structural diversities indicate that the bis(pyridyl) co‐ligands with different flexibility play a key role on the formation of the final supramolecular structures. The complexes were characterized by X‐ray crystallographic, IR, elemental, thermal stability, and powder X‐ray diffraction analyses. In addition, the photoluminescent properties in solid state were also investigated.     

Synthesis and Characterization of [Zn2(4,4′‐bipy)n(AcO)4] – One‐dimensional Chain (n = 1) and One‐dimensional Double‐Chain (n = 2) Coordination Polymers

Two new Zn^II(μ‐4,4′‐bipy) coordination polymers with acetate anions, [Zn(4,4′‐bipy)(AcO)₂] ( 1 ) and [Zn₂(4,4′‐bipy)(AcO)₄] ( 2 ), have been synthesized. The compounds were characterized with elemental analysis, IR‐, ¹H NMR‐, ¹³C NMR spectroscopy and studied by thermal analysis, fluorescence measurements and x‐ray crystallography. The structural studies of compound 1 suggest the structure is a coordination polymer of zinc(II) consisting of linear double chains formed by bridging 4,4′‐bipy ligand and connection of the acetate‐bridged centrosymmetric [Zn₂(OAc)₂]²⁺ nodes.     

Synthesis,Structures, Luminescence,and Magnetic Properties of Two Three‐dimensional Lanthanide Organic Frameworks Comprising Pyrazine‐2,3‐dicarboxylic Acid

Two three‐dimensional (3D) lanthanide coordination polymers (CPs) of the general formula [Ln₂(PDOA)₃(H₂O)]_n · 2nH₂O [Ln = Gd ( 1 ), Tb ( 2 )] were synthesized by solvothermal reactions of the corresponding rare‐earth chloride and pyrazine‐2,3‐dicarboxylic acid (H₂PDOA). The CPs were structurally characterized by single‐crystal X‐ray diffraction, IR spectroscopy, thermogravimetry, and elemental analysis. CPs 1 and 2 are isostructural and crystallize in the monoclinic space group P2₁/c. The frameworks are constructed from dinuclear lanthanide building blocks in which the PDOA^2– ions adopt three coordination modes, μ₃‐kO;kO;kN,O, μ₄‐kN,O;kO;kO;kO,O, and μ₅‐kN,O;kO;kO;kO,O;kO, respectively. The Tb³⁺ polymer of 2 exhibits characteristic photoluminescence in the visible region. The magnetic properties of CP 1 were investigated by measuring the magnetic susceptibilities in the temperature range 1.8–300 K.     

Pseudohalide‐directed Assembly of Two Zinc(II) Coordination Polymers with a 3,4‐Bis(3‐pyridyl)‐5‐(4‐pyridyl)‐1,2,4‐triazole Tecton

The zinc(II) pseudohalide complexes {[Zn(L³³⁴)(SCN)₂(H₂O)](H₂O)₂}_n ( 1 ) and [Zn(L³³⁴)(dca)₂]_n ( 2 ) were synthesized and characterized using the ligand 3,4‐bis(3‐pyridyl)‐5‐(4‐pyridyl)‐1,2,4‐triazole (L³³⁴) and ZnCl₂ in presence of thiocyanate (SCN^–) and dicynamide [dca, N(CN)₂^–] respectively. Single‐crystal X‐ray structural analysis revealed that the central Zn^II atoms in both complexes have similar octahedral arrangement. Compound 1 has a 2D sheet structure bridged by bidentate L³³⁴ and double μ_N,S‐thiocyanate anions, whereas complex 2 , incorporating with two monodentate dicynamide anions, displays a two‐dimensional coordination framework bridged by tetradentate L³³⁴ ligand. Structural analysis demonstrated that the influence of pseudohalide anions plays an important role in determining the resultant structure. Both complexes were characterized by IR spectroscopy, microanalysis, and powder X‐ray diffraction techniques. In addition, the solid fluorescence and thermal stability properties of both complexes were investigated.     

Synthesis,Structures, Magnetic and Luminescent Properties of a Series of Iron(II) and Zinc(II) Coordination Frameworks with Versatile 4‐Substitued 1, 2,4‐Triazole Ligands

Three multi‐dentate 1, 2,4‐triazole derivative ligands containing different 4‐substituted groups, namely N‐1, 2,4‐triazol‐4‐yl(pyridin‐3‐yl)methylenimine (L₁), N‐1, 2,4‐triazol‐ 4‐yl(pyridin‐4‐yl)methylenimine (L₂), and 4‐(2‐pyridine)‐1, 2,4‐triazole (L₃) were used to isolate five iron(II) and zinc(II) coordination frameworks, [Zn(μ₂‐L₁)Cl₂] ( 1 ), [Zn(μ₂‐L₂)Br₂] ( 2 ), [Fe(L₁)₂(NCS)₂(H₂O)₂] ( 3 ), [Fe(L₃)₂(dca)₂(H₂O)₂] ( 4 ), and [Fe(L₃)₂(μ₂‐dca)] ( 5 ) (dca = dicyanamide anion). When different zinc(II) salts were used to react with L₁ and L₂ under solvothermal conditions, two one‐dimensional (1D) zinc(II) coordination frameworks 1 and 2 containing four‐coordinate central zinc(II) atoms were isolated. 1 is a 3D achiral supra‐molecular framework, whereas 2 is a 3D chiral supra‐molecular framework containing helical chains on a 2₁ axis. 3 is a mono‐nuclear iron(II) coordination framework containing six‐coordinate central Fe^II atoms. When L₃ was employed, mono‐nuclear iron(II) framework 4 and 1D iron(II) chain 5 could be isolated when different amounts of Nadca were introduced into the reaction system. Variable‐temperature magnetic susceptibility data of 3 – 5 were recorded in the 2–300 K temperature range indicating weak anti‐ferromagnetic interactions. The solid‐state luminescent properties of coordination polymers 1 and 2 were also investigated at room temperature.     

The X‐ray Single Crystal Structures of an Acid‐functionalized Bis(2‐picolyl)amine (bpa) Ligand with Palladium(II) and Zinc(II) Display Different Intermoleclar Interactions around the Common (H2O)2(anion)2 Motif

This work reports structural investigations on two metal complexes of the functionalized (p‐carboxylatobenzyl)‐bis(2‐picolyl)amine ligand 1 (HL). The complex {[HLPdCl]Cl × H₂O}₂ ( 2_Pd ) has a square‐planar coordination around the Pd ion. It forms discrete dimers by intermolecular hydrogen bonding involving the protonated ligand HL. The coordination around the Zn²⁺ ion in {[(H₂O)LZn]CF₃SO₃ × 2 H₂O}_∞ ( 3_Zn ) is best described as distorted trigonal‐bipyramidal. The N₃O₂ ligand sphere is composed of three nitrogen atoms from the bpa ligand, one water molecule, and a carboxylate oxygen atom from a neighbouring molecule, thus forming infinite chains along the crystallographic a axis. Further intermolecular interactions are based on the same (H₂O)₂(anion)₂ motif as for 2_Pd , but whereas the former forms discrete dimers, 3_Zn forms a more complicated two‐dimensional coordination polymer with additional intermolecular hydrogen bonds.     

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).