A two‐dimensional copper(II) coordination polymer based on 2,4′‐oxybis(benzoate) and 4,4′‐bipyridine

The reaction of Cu(NO₃)₂·3H₂O with 2,4′‐oxybis(benzoic acid) and 4,4′‐bipyridine under hydrothermal conditions produced a new mixed‐ligand two‐dimensional copper(II) coordination polymer, namely poly[[(μ‐4,4′‐bipyridine‐κ²N ,N ′)[μ‐2,4′‐oxybis(benzoato)‐κ⁴O ²,O ^2′:O ⁴,O ^4′]copper(II)] monohydrate], {[Cu(C₁₄H₈O₅)(C₁₀H₈N₂)]·H₂O}_n , which was characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single‐crystal X‐ray diffraction. The X‐ray diffraction crystal structure analysis reveals that the Cu^II ions are connected to form a two‐dimensional wave‐like network through 4,4′‐bipyridine and 2,4′‐oxybis(benzoate) ligands. The two‐dimensional layers are expanded into a three‐dimensional supramolecular structure through intermolecular O—H…O and C—H…O hydrogen bonds. Furthermore, magnetic susceptibility measurements indicate that the complex shows weak antiferromagnetic interactions between adjacent Cu^II ions.     

Two new CdII and ZnII coordination polymers incorporating 1‐aminobenzene‐3,4,5‐tricarboxylic acid: synthesis,crystal structure and characterization

Aminobenzoic acid derivatives are widely used in the preparation of new coordination polymers since they contain O‐atom donors, as well as N‐atom donors, and have a rich variety of coordination modes which can lead to polymers with intriguing structures and interesting properties. Two new coordination polymers incorporating 1‐aminobenzene‐3,4,5‐tricarboxylic acid (H₃abtc), namely, poly[(μ₃‐1‐amino‐5‐carboxybenzene‐3,4‐dicarboxylato)diaquacadmium(II)], [Cd(C₉H₅NO₆)(H₂O)₂]_n, (I), and poly[[bis(μ₅‐1‐aminobenzene‐3,4,5‐tricarboxylato)triaquatrizinc(II)] dihydrate], {[Zn₃(C₉H₄NO₆)₂(H₂O)₃]·2H₂O}_n, (II), have been prepared and structurally characterized by single‐crystal X‐ray diffraction. In polymer (I), each tridentate 1‐amino‐5‐carboxybenzene‐3,4‐dicarboxylate (Habtc^2?) ligand coordinates to three Cd^II ions to form a two‐dimensional network structure, in which all of the Cd^II ions and Habtc^2? ligands are equivalent, respectively. Polymer (II) also exhibits a two‐dimensional network structure, in which three crystallographically independent Zn^II ions are bridged by two crystallographically independent pentadentate 1‐aminobenzene‐3,4,5‐tricarboxylate (abtc^3?) ligands. This indicates that changing the metal ion can influence the coordination mode of the H₃abtc‐derived ligand and further influence the detailed architecture of the polymer. Moreover, the IR spectra, thermogravimetric analyses and fluorescence properties were investigated.     

A one‐dimensional cobalt(II) coordination polymer based on 2,4′‐oxydibenzoic acid: poly[[[diaquabis[2‐(4‐carboxyphenoxy)benzoato‐κO1]cobalt(II)]‐μ‐4,4′‐bipyridine‐κ2N:N′] dihydrate]

The reaction of CoSO₄ with 2,4‐oxydibenzoic acid (H₂oba) and 4,4′‐bipyridine (bipy) under hydrothermal condition yielded a new one‐dimensional cobalt(II) coordination polymer, {[Co(C₁₄H₉O₅)₂(C₁₀H₈N₂)(H₂O)₂]·2H₂O}_n, which was characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, magnetic properties and single‐crystal X‐ray diffraction. The Co^II ions are connected by bipy ligands into infinite one‐dimensional chains. The Hoba⁻ ligands extend out from the two sides of the one‐dimensional chain. O—H...O hydrogen bonding extends these chains into a two‐dimensional supramolecular architecture.     

A new three‐dimensional coordination polymer of SrII based on dipicolinic acid,with different coordination environments for SrII

A three‐dimensional coordination polymer of Sr^II based on dipicolinic acid (pydcH₂) has been synthesized and characterized, namely poly[[diaquabis(μ₃‐6‐carboxypyridine‐2‐carboxylato)bis(μ₄‐pyridine‐2,6‐dicarboxylato)tristrontium(II)] dihydrate], {[Sr₃(C₇H₃NO₄)₂(C₇H₄NO₄)₂(H₂O)₂]·2H₂O}_n. The asymmetric unit consists of two unique Sr^II centres (one of them situated on an inversion centre), two independent pydc²⁻ ligands, and one coordinated and one uncoordinated water molecule. The two independent Sr^II cations are surrounded by water and dipicolinate molecules in distorted square‐antiprism and distorted tricapped trigonal prismatic geometries. The dipicolinate ligands adopt μ₃‐ and μ₄‐bridging modes, linking the alkaline earth metal centres into a three‐dimensional coordination framework. One dipicolinate ligand is doubly deprotonated, while the other is singly deprotonated.     

A three‐dimensional ZnII coordination network based on 5,5′‐methylenebis(2,4,6‐trimethylisophthalic acid) and 2,7‐bis(1H‐imidazol‐1‐yl)fluorene: synthesis,structure and luminescence properties

In recent years, coordination polymers constructed from multidentate carboxylate ligands and N‐containing ligands have attracted much attention since these ligands can adopt a rich variety of coordination modes which can lead to crystalline products with intriguing structures and interesting properties. A new coordination polymer, namely poly[[diaqua[μ‐2,7‐bis(1H‐imidazol‐1‐yl)fluorene‐κ²N³:N^3′][μ‐5,5′‐methylenebis(3‐carboxy‐2,4,6‐trimethylbenzoato)‐κ²O¹:O^1′]zinc(II)] hemihydrate], {[Zn(C₂₃H₂₂O₈)(C₁₉H₁₄N₄)(H₂O)₂]·0.5H₂O}_n, 1 , was prepared by the self‐assembly of Zn(NO₃)₂·6H₂O with 5,5′‐methylenebis(2,4,6‐trimethylisophthalic acid) (H₄BTMIPA) and 2,7‐bis(1H‐imidazol‐1‐yl)fluorene (BIF) under solvothermal conditions. The structure of 1 was determined by elemental analysis, single‐crystal X‐ray crystallography, powder X‐ray diffraction, IR spectroscopy and thermogravimetric analysis. Each Zn^II ion is six‐coordinated by two O atoms from two H₂BTMIPA^2? ligands, by two N atoms from two BIF ligands and by two water molecules, forming a distorted octahedral ZnN₂O₄ coordination geometry. Adjacent Zn^II ions are linked by H₂BTMIPA^2? ligands and BIF ligands, leading to the formation of a two‐dimensional (2D) (4,4)‐ sql network, and intermolecular hydrogen‐bonding interactions connect the 2D layer structure into the three‐dimensional (3D) supramolecular structure. Each 2D layer contains two kinds of helices with the same direction, which are opposite in adjacent layers. The luminescence properties of complex 1 in the solid state have also been investigated.     

A Copper‐Carboxylate Layer‐Framework with Pseudo‐­Kagomé Net

A two dimensional coordination polymer with pseudo‐Kagomé net [Cu₃(btc)₂(NH₃)₈(H₂O)] was prepared from Cu(NO₃)₂ · 3H₂O and 1, 3, 5‐benzenetricarboxylic acid (btc) in ammonia aqua solution and was structurally characterized by X‐ray diffraction. The magnetic susceptibility measurements, measured from 2 to 300 K, revealed a weak anti‐ferromagnetic interaction between the Cu^II ions via the btc ligands.     

Synthesis and Structural Characterization of One‐Dimensional Cadmium(II) Coordination Polymers Containing Polydentate Nitrogen Ligands

The reactions of Cd(NO₃)₂·4H₂O with NH₄SCN and 2,4‐dpa (2,4‐dpa = 2,4‐dipyridineamine) in CH₃OH afforded the one‐dimensional coordination polymer [Cd(NCS)₂(2,4‐dpa)₂]_n, 1 , while reaction of Cd(NO₃)₂·4H₂O with NH₄SCN and PmPa (PmPa = 2‐(1‐piperazinyl)pyrimidine) in CH₃OH gave complex of the type [Cd(NCS)₂(PmPa)₂]_n, 2. Each of the 2,4‐dpa ligand in complex 1 is coordinated to the Cd²⁺ metal center through pyridyl nitrogen atoms to form the one‐dimensional chain structures. The distorted {CdN4S2} octahedral coordination geometry around Cd²⁺ center is completed by pairs of bidentate thiocyanato ligands. Complex 2 has the 1‐D arrangement constructed through one‐dimensional double μ(N,S) end‐to‐end bridging thiocyanato groups bridged Cd(II) chains interconnected through PmPa ligands.     

A three‐dimensional cadmium coordination polymer based on 1,4‐bis(1,2,4‐triazol‐1‐yl)but‐2‐ene and benzene‐1,3,5‐tricarboxylic acid

The Cd^II three‐dimensional coordination poly[[[μ₄‐1,4‐bis(1,2,4‐triazol‐1‐yl)but‐2‐ene]bis(μ₃‐5‐carboxybenzene‐1,3‐dicarboxylato)dicadmium(II)] dihydrate], {[Cd₂(C₉H₄O₆)₂(C₈H₁₀N₆)]·2H₂O}_n , (I), has been synthesized by the hydrothermal reaction of Cd(NO₃)₂·4H₂O, benzene‐1,3,5‐tricarboxylic acid (1,3,5‐H₃BTC) and 1,4‐bis(1,2,4‐triazol‐1‐yl)but‐2‐ene (1,4‐btbe). The IR spectrum suggests the presence of protonated carboxylic acid, deprotonated carboxylate and triazolyl groups. The purity of the bulk sample was confirmed by elemental analysis and X‐ray powder diffraction. Single‐crystal X‐ray diffraction analysis reveals that the Cd^II ions adopt a five‐coordinated distorted trigonal–bipyramidal geometry, coordinated by three O atoms from three different 1,3,5‐HBTC²⁻ ligands and two N atoms from two different 1,4‐btbe ligands; the latter are situated on centres of inversion. The Cd^II centres are bridged by 1,3,5‐HBTC²⁻ and 1,4‐btbe ligands into an overall three‐dimensional framework. When the Cd^II centres and the tetradentate 1,4‐btbe ligands are regarded as nodes, the three‐dimensional topology can be simplified as a binodal 4,6‐connected network. Thermogravimetric analysis confirms the presence of lattice water in (I). Photoluminescence studies imply that the emission of (I) may be ascribed to intraligand fluorescence.     

Synthesis and characterization of two one‐dimensional CdII coordination polymers (CPs) with 5‐amino‐2,4,6‐tribromoisophthalic acid and flexible N‐donor bipyridyl ligands

The bromo‐substituted aromatic dicarboxylic acid 5‐amino‐2,4,6‐tribromoisophthalic acid (H₂ATBIP) was used to assemble with Cd^II ions in the presence of the N‐donor flexible bipyridyl ligands 3,3′‐(diazene‐1,2‐diyl)dipyridine (mzpy) and 1,3‐bis(pyridin‐3‐ylmethyl)urea (3bpmu), leading to the formation of two chain coordination polymers by adopting solution methods, namely, catena‐poly[[[triaqua(5‐amino‐2,4,6‐tribromoisophthalato‐κO)cadmium(II)]‐μ‐3,3′‐(diazene‐1,2‐diyl)dipyridine‐κ²N¹:N^1′] dihydrate], {[Cd(C₈H₂Br₃NO₄)(C₁₀H₈N₄)(H₂O)₃]·2H₂O}_n or {[Cd(ATBIP)(mzpy)(H₂O)₃]·2H₂O}_n, ( 1 ), and catena‐poly[[[tetraaquacadmium(II)]‐μ‐1,3‐bis(pyridin‐3‐ylmethyl)urea‐κ²N¹:N^1′‐[diaquabis(5‐amino‐2,4,6‐tribromoisophthalato‐κO)cadmium(II)]‐μ‐1,3‐bis(pyridin‐3‐ylmethyl)urea‐κ²N¹:N^1′] octahydrate], {[Cd(C₈H₂Br₃NO₄)(C₁₂H₁₂N₄O)(H₂O)₃]·4H₂O}_n or {[Cd(ATBIP)(3bpmu)(H₂O)₃]·4H₂O}_n, ( 2 ). Both complexes were characterized by FT–IR spectroscopic analysis, thermogravimetric analysis (TGA), solid‐state diffuse reflectance UV–Vis spectroscopic analysis, and single‐crystal and powder X‐ray diffraction analysis (PXRD). The mzpy and 3bpmu ligands bridge the Cd^II metal centres in ( 1 ) and ( 2 ) into one‐dimensional chains, and the ATBIP²⁻ ligands show a monodentate coordination to the Cd^II centres in both coordination polymers. A discrete water tetramer exists in ( 1 ). Within the chains of ( 1 ) and ( 2 ), there are halogen bonds between adjacent ATBIP²⁻ and mzpy or 3bpmu ligands, as well as hydrogen bonds between the ATBIP²⁻ ligands and the coordinated water molecules. With the aid of weak interactions, the structures of ( 1 ) and ( 2 ) are further extended into three‐dimensional supramolecular networks. An analysis of the solid‐state diffuse reflectance UV–Vis spectra of ( 1 ) and ( 2 ) indicates that a wide indirect band gap exists in both complexes. Complexes ( 1 ) and ( 2 ) exhibit irreversible and reversible dehydration–rehydration behaviours, respectively, and the solid‐state fluorescence properties of both complexes have been studied.     

A novel three‐dimensional tetranuclear CoII coordination polymer with water hexamers based on the V‐shaped tetracarboxylate ligand 4‐(2,4‐dicarboxylatophenoxy)phthalate

A new coordination polymer (CP), namely, poly[[diaquatris[μ₂‐1,4‐bis(1H‐imidazol‐1‐yl)benzene]bis[μ₆‐4‐(2,4‐dicarboxylatophenoxy)phthalato]tetracobalt(II)] hexahydrate], {[Co₄(C₁₆H₆O₉)₂(C₁₂H₁₀N₄)₃(H₂O)₂]·6H₂O}_n, has been synthesized by solvothermal reaction. The CP was fully characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, and powder and single‐crystal X‐ray diffraction. It presents a three‐dimensional (3D) structure based on tetranuclear Co^II secondary building units (SBUs) with a tfz‐d net and point symbol (4³)₂(4⁶·6¹⁸·8⁴). The 4‐(2,4‐dicarboxyphenoxy)phthalic acid (H₄dcppa) ligands are completely deprotonated and link {Co₄(COO)₄}^4? SBUs into two‐dimensional (2D) layers. Furthermore, adjacent layers are connected by 1,4‐bis(1H‐imidazol‐1‐yl)benzene (bib) ligands, giving rise to a 3D supramolecular architecture. Interestingly, there are numerous elliptical cavities in the CP where isolated unique discrete hexameric water clusters have been observed. The results of thermogravimetric and magnetic analyses are described in detail.     

Construction and photoluminescence properties of a three‐dimensional ZnII coordination network based on naphthalene‐1,4‐dicarboxylic acid and 1,6‐bis(pyridin‐3‐yl)‐1,3,5‐hexatriene

In recent years, coordination polymers constructed from multidentate carboxylate and pyridyl ligands have attracted much attention because these ligands can adopt a rich variety of coordination modes and thus lead to the formation of crystalline products with intriguing structures and interesting properties. A new coordination polymer, namely poly[[μ₂‐1,6‐bis(pyridin‐3‐yl)‐1,3,5‐hexatriene‐κ²N:N′](μ₃‐naphthalene‐1,4‐dicarboxylato‐κ⁴O¹,O^1′:O⁴:O^4′)zinc(II)], [Zn(C₁₂H₆O₄)(C₁₆H₁₄N₂)]_n, has been prepared by the self‐assembly of Zn(NO₃)₂·6H₂O, naphthalene‐1,4‐dicarboxylic acid (1,4‐H₂ndc) and 1,6‐bis(pyridin‐3‐yl)‐1,3,5‐hexatriene (3,3′‐bphte) under hydrothermal conditions. The title compound has been structurally characterized by IR spectroscopy, elemental analysis, powder X‐ray diffraction and single‐crystal X‐ray diffraction analysis. Each Zn^II ion is six‐coordinated by four O atoms from three 1,4‐ndc²⁻ ligands and by two N atoms from two 3,3′‐bphte ligands, forming a distorted octahedral ZnO₄N₂ coordination geometry. Pairs of Zn^II ions are linked by 1,4‐ndc²⁻ ligands, leading to the formation of a two‐dimensional square lattice ( sql ) layer extending in the ab plane. In the crystal, adjacent layers are further connected by 3,3′‐bphte bridges, generating a three‐dimensional architecture. From a topological viewpoint, if each dinuclear zinc unit is considered as a 6‐connected node and the 1,4‐ndc²⁻ and 3,3′‐bphte ligands are regarded as linkers, the structure can be simplified as a unique three‐dimensional 6‐connected framework with the point symbol 4⁴6¹⁰8. The thermal stability and solid‐state photoluminescence properties have also been investigated.     

catena‐Poly[[[(iminodiacetato‐κO)silver(I)]‐μ3‐2‐aminopyrimidine‐κ3N1:N2:N3] monohydrate]: a one‐dimensional silver(I) coordination polymer with mixed ligands

The title compound, {[Ag(C₄H₆NO₄)(C₄H₅N₃)]·H₂O}_n, was synthesized by the reaction of silver(I) nitrate with 2‐aminopyrimidine and iminodiacetic acid. X‐ray analysis reveals that the crystal structure contains a one‐dimensional ladder‐like Ag^I coordination polymer and that N—H...O and O—H...O hydrogen bonding results in a three‐dimensional network. The Ag^I centre is four‐coordinated by three N atoms from three different 2‐aminopyrimidine ligands and one O atom from one iminodiacetate ligand. Comparison of the structural features with previous findings suggests that the existence of a second ligand plays an important role in the construction of such polymer frameworks.     

A three‐dimensional cyanide‐bridged heterometallic coordination polymer: poly[[diacetonitrilediaqua[μ2‐3,6‐bis(pyridin‐2‐yl)‐1,2,4,5‐tetrazine‐κ4N1,N6:N3,N4]tetra‐μ‐cyanido‐tetracyanidodimanganese(II)molybdate(IV)] dihydrate]

A metal coordination polymer, {[Mn₂Mo(CN)₈(C₁₂H₈N₆)(CH₃CN)₂(H₂O)₂]·2H₂O}_n, has been synthesized by the reaction of Mn(ClO₄)₂·6H₂O with 3,6‐bis(pyridin‐2‐yl)‐1,2,4,5‐tetrazine (bptz) and (Bu₃N)₃[Mo(CN)₈] at room temperature. The polymer was characterized by IR spectroscopy, elemental analysis and X‐ray diffraction, and the magnetic properties were also investigated. The X‐ray diffraction analysis reveals that the compound is a new three‐dimensional coordination polymer with a PtS‐type network. Magnetic investigation shows antiferromagnetic coupling between adjacent Mn²⁺ cations.     

Polypropylene and poly(ethylene‐co‐1‐octene) effective synthesis with diamine‐bis(phenolate) complexes: Effect of complex structure on catalyst activity and product microstructure

A series of group 4 metal complexes bearing amine‐bis(phenolate) ligands with the amino side‐arm donor: (μ‐O)[Me₂N(CH₂)₂N(CH₂‐2‐O‐3,5‐tBu₂‐C₆H₂)₂ZrCl]₂ ( 1a ), R₂N(CH₂)₂N(CH₂‐2‐O‐3‐R¹‐5‐R²‐C₆H₂)₂TiCl₂ (R = Me, R¹, R² = tBu ( 2a ), R = iPr, R¹, R² = tBu ( 2b ), R = iPr, R¹ = tBu, R² = OMe ( 2c )), and Me₂N(CH₂)₂N(CH₂‐2‐O‐3,5‐tBu₂‐C₆H₂)(CH₂‐2‐O‐C₆H₄)TiCl₂ ( 2d ) are used in ethylene and propylene homopolymerization, and ethylene/1‐octene copolymerization. All complexes, upon their activation with Al(iBu)₃/Ph₃CB(C₆F₅)₄, exhibit reasonable catalytic activity for ethylene homo‐ and copolymerization giving linear polyethylene with high to ultra‐high molecular weight (600·× 10³–3600·× 10³ g/mol). The activity of 1a /Al(iBu)₃/Ph₃CB(C₆F₅)₄ shows a positive comonomer effect, leading to over 400% increase of the polymer yield, while the addition of 1‐octene causes a slight reduction of the activity of the complexes 2a‐2d . The complexes with the NMe₂ donor group ( 2a , 2d , 1a ) display a high ability to incorporate a comonomer (up to 9–22 mol%), and the use of a bulkier donor group, N(iPr)₂ ( 2b , 2c ), results in a lower 1‐octene incorporation. All the produced copolymers reveal a broad chemical composition distribution. In addition, the investigated complexes polymerized propylene with the moderate ( 1a , 2a ) to low ( 2b‐2d ) activity, giving polymers with different microstructures, from purely atactic to isotactically enriched (mmmm = 28%). © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2467–2476     

Syntheses,Structures, and Photoluminescence Properties of a Series of 3D Zn‐Ln Heterometallic Complexes with 2,3‐Pyrazine Dicarboxylic Acid as a Bridging Ligand

A series of 3D d–f heterometallic coordination polymers, {[Ln₂Zn(Pzdc)₄(H₂O)₆] · 2H₂O}_n [Ln = La ( 1 ), Pr ( 2 ), Nd ( 3 ), Sm ( 4 ), Eu ( 5 ), Gd ( 6 ), Tb ( 7 ), Dy ( 8 )] (H₂Pzdc = 2,3‐pyrazine dicarboxylic acid), were synthesized by one‐pot reactions under hydrothermal conditions. X‐ray crystallographical analysis and powder X‐ray diffraction analysis reveal that the complexes 1 – 8 are isostructural and adopt a multi‐parallel quadrilateral channel network structure with {4.6 · 2}₂{4 · 2.6 · 2.8 · 2}{6 · 3}2{6 · 5.8}₂ topology, in which the central Ln^III ion is nine‐coordinate by four oxygen atoms and two nitrogen atoms from four ligands and three oxygen atoms from three coordinated H₂O molecules and the central Zn^II ion is six‐coordinate by four oxygen atoms and two nitrogen atoms from four ligands. Moreover, the photophysical properties related to the electronic transition for complexes 4 , 5 , 7 , and 8 were investigated by the excitation and emission spectra as well as the emission lifetimes.     

Synthesis and characterization of two isostructural 3d–4f coordination compounds based on pyridine‐2,6‐dicarboxylic acid and 4,4′‐bipyridine

The design and synthesis of 3d–4f heterometallic coordination polymers have attracted much interest due to the intriguing diversity of their architectures and topologies. Pyridine‐2,6‐dicarboxylic acid (H₂pydc) has a versatile coordination mode and has been used to construct multinuclear and heterometallic compounds. Two isostructural centrosymmetric 3d–4f coordination compounds constructed from pyridine‐2,6‐dicarboxylic acid and 4,4′‐bipyridine (bpy), namely 4,4′‐bipyridine‐1,1′‐diium diaquabis(μ₂‐pyridine‐2,6‐dicarboxylato)tetrakis(pyridine‐2,6‐dicarboxylato)bis[4‐(pyridin‐4‐yl)pyridinium]cobalt(II)dieuropium(III) octahydrate, (C₁₀H₁₀N₂)[CoEu₂(C₁₀H₉N₂)₂(C₇H₃NO₄)₆(H₂O)₂]·8H₂O, (I), and 4,4′‐bipyridine‐1,1′‐diium diaquabis(μ₂‐pyridine‐2,6‐dicarboxylato)tetrakis(pyridine‐2,6‐dicarboxylato)bis[4‐(pyridin‐4‐yl)pyridinium]cobalt(II)diterbium(III) octahydrate, (C₁₀H₁₀N₂)[CoTb₂(C₁₀H₉N₂)₂(C₇H₃NO₄)₆(H₂O)₂]·8H₂O, (II), were synthesized under hydrothermal conditions and characterized by IR and fluorescence spectroscopy, thermogravimetric analysis and powder X‐ray diffraction. Both compounds crystallize in the triclinic space group P. The Eu^III and Tb^III cations adopt nine‐coordinated distorted tricapped trigonal–prismatic geometries bridged by three pydc^2? ligands. The Co^II cation has a six‐coordination environment formed by two pydc^2? ligands, two bpy ligands and two coordinated water molecules. Adjacent molecules are connected by π–π stacking interactions to form a one‐dimensional chain, which is further extended into a three‐dimensional supramolecular network by multipoint hydrogen bonds.     

One‐dimensional copper(II) coordination polymers based on 1,3‐bis(pyridin‐4‐yl)propane and diimine ligands

Two one‐dimensional (1D) coordination polymers (CPs), namely catena‐poly[[[aqua(2,2′‐bipyridine‐κ²N,N′)(nitrato‐κO)copper(II)]‐μ‐1,3‐bis(pyridin‐4‐yl)propane‐κ²N:N′] nitrate], {[Cu(NO₃)(C₁₀H₈N₂)(C₁₃H₁₄N₂)(H₂O)]·NO₃}_n ( 1 ), and catena‐poly[[[aqua(nitrato‐κO)(1,10‐phenanthroline‐κ²N,N′)copper(II)]‐μ‐1,3‐bis(pyridin‐4‐yl)propane‐κ²N:N′] nitrate], {[Cu(NO₃)(C₁₂H₈N₂)(C₁₃H₁₄N₂)(H₂O)]·NO₃}_n ( 2 ), have been synthesized using [Cu(NO₃)(NN)(H₂O)₂]NO₃, where NN = 2,2′‐bipyridine (bpy) or 1,10‐phenanthroline (phen), as a linker in a 1:1 molar ratio. The CPs were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single‐crystal X‐ray structure determination. The 1,3‐bis(pyridin‐4‐yl)propane (dpp) ligand acts as a bridging ligand, leading to the formation of a 1D polymer. The octahedral coordination sphere around copper consists of two N atoms from bpy for 1 or phen for 2 , two N atoms from dpp, one O atom from water and one O atom from a coordinated nitrate anion. Each structure contains two crystallographically independent chains in the asymmetric unit and the chains are linked via hydrogen bonds into a three‐dimensional network.     

A one‐dimensional silver(I) coordination polymer based on 5‐methyl‐1,3,4‐thiadiazol‐2‐amine and pyridine‐2,3‐dicarboxylate

The bifunctional pyridine‐2,3‐dicarboxylic acid (H₂pdc) ligand has one N atom and four O atoms, which could bind more than one Ag^I centre with diverse binding modes. A novel infinite one‐dimensional Ag^I coordination polymer, namely catena‐poly[[silver(I)‐(μ₂‐pyridine‐2,3‐dicarboxylato‐κ²N :O ³)‐silver(I)‐tris(μ₂‐5‐methyl‐1,3,4‐thiodiazol‐2‐amine‐κ²N :N ′)] monohydrate ethanol monosolvate], {[Ag₂(C₇H₃NO₄)(C₃H₅N₃S)₃]·H₂O·C₂H₅OH}_n , has been synthesized using H₂pdc and 5‐methyl‐1,3,4‐thiadiazol‐2‐amine (tda), and characterized by single‐crystal X‐ray diffraction. One Ag^I atom is located in a four‐coordinated AgN₄ tetrahedral geometry and the other Ag^I atom is in a tetrahedral AgN₃O geometry. A dinuclear Ag^I cluster formed by three tda ligands with a paddelwheel configuration is bridged by the dianionic pdc²⁻ ligand into a one‐dimensional coordination polymer. Interchain N—H…O hydrogen bonds extend the one‐dimensional chains into an undulating two‐dimensional sheet. The sheets are further packed into a three‐dimensional supramolecular framework by interchain N—H…O hydrogen bonds.     

Co‐crystals based on 1,2,4,5‐Benzenetetracarboxylic Acid: Synthesis,Supramolecular Frameworks and Optical Properties

Two new co‐crystals based on 1,2,4,5‐benzenetetracarboxylic acid, (H₂BETC)(H₄tpim)](NO₃) ( 1 ) and [(H₄BETC)_0.5(H₂BETC)_0.5(HVB4)](H₂O) ( 2 ) [H₄BETC = 1,2,4,5‐benzenetetracarboxylic acid, Htpim = 2,4,5‐tri(4‐pyridyl)‐imidazole, and VB4 = adenine], were synthesized and characterized by elemental analyses, IR spectroscopy, single‐crystal X‐ray diffraction, and X‐ray powder diffraction analysis. Compounds 1 and 2 were further assembled to form 3D supramolecular frameworks with 1D channels by intermolecular C–H ··· O, O–H ··· O, and N–H ··· O hydrogen‐bonding interactions. The results reveal that the structural differences of 1 and 2 may be attributed to different molecular components. Moreover, the UV/Vis and luminescent spectra of ligands and corresponding compounds were briefly investigated.     

Construction and photocatalytic properties of two metal‐mediated coordination polymers based on benzene‐1,3,5‐tricarboxylic acid and trans‐1‐(pyridin‐3‐yl)‐2‐(pyridin‐4‐yl)ethene

With the rapid development of modern industry, water pollution has become an intractable environmental issue facing humans worldwide. In particular, the organic dyes discharged into natural water from dyestuffs, dyeing and the textile industry are the main sources of pollution in wastewater. To eliminate these types of pollutants, degradation of organic contaminants through a photocatalytic technique is an effective methodology. To exploit more crystalline photocatalysts for the degradation of organic dyes, two coordination polymers, namely catena‐poly[[(3,5‐dicarboxybenzene‐1‐carboxylato‐κO ¹)silver(I)]‐μ‐trans‐1‐(pyridin‐3‐yl)‐2‐(pyridin‐4‐yl)ethene‐κ²N :N ′], [Ag(C₉H₅O₆)(C₁₂H₁₀N₂)]_n or [Ag(H₂BTC)(3,4′‐bpe)]_n , (I), and poly[[(μ₃‐5‐carboxybenzene‐1,3‐dicarboxylato‐κ⁴O ¹,O ^1′:O ³:O ³)[μ‐trans‐1‐(pyridin‐3‐yl)‐2‐(pyridin‐4‐yl)ethene‐κ²N :N′ ]cadmium(II)] monohydrate], {[Cd(C₉H₄O₆)(C₁₂H₁₀N₂)]·H₂O}_n or {[Cd(HBTC)(3,4′‐bpe)]·H₂O}_n , (II), have been prepared by the hydrothermal reactions of benzene‐1,3,5‐tricarboxylic acid (H₃BTC) and trans‐1‐(pyridin‐3‐yl)‐2‐(pyridin‐4‐yl)ethene (3,4′‐bpe) in the presence of AgNO₃ or Cd(NO₃)₂·4H₂O, respectively. These two title compounds have been structurally characterized by IR spectroscopy, elemental analysis, single‐crystal X‐ray diffraction and powder X‐ray diffraction. In (I), the Ag^I ions and organic ligands form a one‐dimensional coordination chain, and adjacent coordination chains are connected by Ag…O interactions to give rise to a two‐dimensional supramolecular network. Each two‐dimensional network is entangled with other equivalent networks to generate an infrequent interlocked 2D→3D (2D and 3D are two‐ and three‐dimensional, respectively) supramolecular framework. In (II), the Cd^II ions are bridged by the HBTC²⁻ and 3,4′‐bpe ligands, which lie across centres of inversion, to give a two‐dimensional coordination network. The thermal stabilities and photocatalytic properties of the title compounds have also been studied.