Cadmium(II) Complexes with a Bulky Anthracene‐based Carboxylate Ligand: Syntheses,Crystal Structures,and Luminescent Properties

To explore the coordination possibilities of anthracene‐based ligands, three cadmium(ιι) complexes with anthracene‐9‐carboxylate ( L ) and relevant auxiliary chelating or bridging ligands were synthesized and characterized: Cd₂( L )₄(2bpy)₂(μ‐H₂O) ( 1 ), Cd₂( L )₄(phen)₂(μ‐H₂O) ( 2 ), and {[Cd₃( L )₆(4bpy)]}_∞ ( 3 ) (2bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline, and 4bpy = 4,4′‐bipyridine). Structural analyses show that complexes 1 and 2 both take dinuclear structures by incorporating the chelating 2bpy or phen ligand, which are further interlinked by intermolecular hydrogen‐bonding, π ··· π stacking, and/or C–H ··· π supramolecular interactions to generate higher‐dimensional supramolecular frameworks. Complex 3 has a one‐dimensional (1D) ribbon‐like structure, which is further assembled into a two‐dimensional (2D) layer, and a three‐dimensional (3D) framework by the co‐effects of interchain C–H ··· O hydrogen‐bonding and C–H ··· π supramolecular interactions. Moreover, the luminescent properties of these complexes were further investigated in detail.     

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 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.     

A Novel μ2‐(H2O)‐Bridged Double‐Chain Coordination Polymer [Cd(pc)(phen)(H2O)]n with Rhombic Grids (H2pc = pamoic acid,phen = 1,10‐phenanthroline)

A novel coordination polymer [Cd(pc)(phen)(H₂O)]_n (H₂pc = pamoic acid, phen = 1,10‐phenanthroline) has been synthesized under hydrothermal conditions. Single crystal X‐ray diffraction analysis reveals that the compound crystallizes in triclinic space group P1. All the Cd^II atoms in the compound are hexacoordinate and are linked by pamoicate ligands to form a one‐dimensional zigzag chain. Furthermore, two adjacent zigzag chains are connected by the μ₂‐(H₂O) molecules to form a double‐chain with rhombic grids. There exist intermolecular C–H ··· π contacts, π–π stacking and hydrogen‐bonding interactions. Compound 1 displays strong fluorescent emission in the solid state 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2,4′-二羧基二苯甲酮构筑的具有一维梯状链和一维隧道的三维超分子体系

采用水热法设计合成了两个新型三维超分子化合物H₂L·H₂O (1)和[Ag(bpy)₂]·HL·H₂O (2) (其中bpy=2,2'-联吡啶, H₂L=2,4′-二羧基二苯甲酮),晶体结构分析表明,它们均是通过氢键采用不同的连接方式拓展而成。其中,化合物1 是2,4′-二羧基二苯甲酮和水分子通过O–H···O氢键形成的一维梯状链扩展构筑的三维超分子体系;化合物2 则是2,4′-二羧基二苯甲酮和水分子通过两种氢键形成含有一维隧道的三维超分子体系。有趣的是,[Ag(bpy)₂]⁺ 阳离子通过π–π 堆积和弱的Ag···Ag相互作用连在一起,进而以客体形式填充其中。荧光性质研究表明,由于存在bpy的螯合与堆积效应,化合物2相比配体和化合物1,其荧光发射峰发生红移。     

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.     

Supramolecular Structures with the 2‐Propyl‐4,5‐dicarboxy‐1H‐imidazole Ligand: Hydrothermal Synthesis,Structures, and Photoluminescence

Self‐assembly of the rigid organic ligand 2‐propyl‐4,5‐dicarboxy‐1H‐imidazole ( L ) with different metal ions (Zn²⁺, Ni²⁺, Cu²⁺, Cd²⁺) led to four new complexes, namely, [M( L )(phen)] [M = Zn ( 1 ); Ni ( 2 ); Cd ( 3 )] and [Cu( L )( 4 )] (phen = 1,10‐phenanthroline). Their structures were determined by single‐crystal X‐ray diffraction analyses, and they were further characterized by elemental analysis, IR spectroscopy, and thermogravimetric analysis. Whereas compounds 1 , 2 , and 3 are discrete units, hydrogen‐bonding interactions play a vital role in these complexes. Compounds 1 and 2 form one‐dimensional (1D) and two‐dimensional (2D) structures through hydrogen‐bondinginteractions with helical character. In 1 , the hydrogen bonds (O–H ··· O) alternately bridge the M^II cations of the discrete units to form a one‐dimensional (1D) infinite helical chain. Complex 2 forms a 2D helical layer through parallel hydrogen bonds (N/O–H ··· O/N) between two adjacent helical chains. In 3 , the hydrogen bonds (N–H ··· O) connect adjacent discrete units into a ten‐membered ring with extension into a one‐dimensional double‐chain supramolecular structure. Complex 4 is a two‐dimensional gridlike (4,4) topological layer which is extended to a 3D network by hydrogen bonding. The solid‐state fluorescence spectrum of complex 3 was determined.     

Crystal Structures and Photoluminescence Properties of Zinc(II) and Cadmium(II) Coordination Polymers with “Y”‐Shaped Ligands

Three Zn^II and Cd^II complexes with Y‐shaped dicarboxylate ligands, namely [Zn(L₁)(2,2′‐bpy)₂(H₂O)] · 2H₂O ( 1 ), [Zn(L₁)(bpp)(H₂O)] ( 2 ), and [Cd(L₁)(H₂O)] · H₂O ( 3 ) [H₂L₁ = N‐phenyliminodiacetic acid, 2,2′‐bpy = 2,2′‐bipyridine, bpp = 1,3‐bis(4‐pyridyl)propane] were synthesized and characterized by elemental analysis, IR spectroscopy single‐crystal X‐ray diffraction, and thermogravimetric analyses. Compound 1 shows an hydrogen‐bonded 2D network, whereas compound 2 is an infinite 1D wavy chain structure, though O–H ··· O hydrogen‐bonded to form a 2D network. Compound 3 displays a 2D uninodal 3‐connected Shubnikov plane net with the point symbol of (4.8²). Moreover, the solid‐state such as thermal stabilities and fluorescence properties of 1 – 3 were also investigated.     

A Polymeric Arched Chain and a Chair‐like M2L2‐Metallamacrocycle Crystal Engineered of [M(phen)]2+ (M = Cu,Cd; phen = 1,10‐Phenanthroline) Corner Units and the Bent Ligand 4,4′‐Dithiodipyridine

Self‐assembly of Cd(phen)²⁺ and Cu(phen)²⁺ (phen = 1,10‐phenanthroline) building blocks with the bent ligand 4,4′‐dithiodipyridine (dtdp) has been investigated. Both building blocks serve as corner units with constrained cis‐geometry. The arched chain coordination polymer [{Cd(phen)(μ‐dtdp)(dtdp)(H₂O)}(ClO₄)₂·2CH₃OH·1.5H₂O]_n ( 1 ) crystallised from a mixture of Cd(ClO₄)₂·H₂O, phen and dtdp in methanol. The reaction of [Cu(phen)(H₂O)₂](CF₃SO₃)₂ ( 2 ) with dtdp in an ethanol/water mixture yielded a chair‐like metallamacrocycle, [{Cu(phen)(CF₃SO₃)₂}₂(μ‐dtpd)₂] ( 3 ). The crystal structure of the precursor complex 2 is also reported.     

Synthesis,Crystal Structures,and Photoluminescence of Lanthanide Coordination Polymers with 4‐Acetamidobenzoate

The reactions of Ln(NO₃)₃ · 6H₂O and 4‐acetamidobenzoic acid (Haba) with 4,4′‐bipyridine (4,4′‐bpy) in ethanol solution resulted in three new lanthanide coordination polymers, namely {[Ln(aba)₃(H₂O)₂] · 0.5(4,4′‐bpy) · 2H₂O}_∞ [Ln = Sm ( 1 ), Gd ( 2 ), and Er ( 3 ), aba = 4‐acetamidobenzoate]. Compounds 1 – 3 are isomorphous and have one‐dimensional chains bridged by four aba anions. 4,4′‐Bipyridine molecules don’t take part in the coordination with Ln^III ions and occur in the lattice as guest molecules. Moreover, the adjacent 1D chains in the complex are further linked through numerous N–H ··· O and O–H ··· O hydrogen bonds to form a 3D supramolecular network. In addition, complex 1 in the solid state shows characteristic emission in the visible region at room temperature.     

Syntheses,Structures and Properties of Four New Transitional Metal Complexes Based on Benzotriazole‐5‐carboxylic Acid

Four new complexes, [Zn(btca)(2,2′‐bpy)] ( 1 ), [Mn(btca)(2,2′‐bpy)] ( 2 ), [Co(btca)(phen)] ( 3 ), and [Cu(btca)(phen)] ( 4 ), (H₂btca=benzotriazole‐5‐carboxylic acid, 2,2′‐bpy=2,2′‐bipyridine, phen=1,10‐phenanthroline), were successfully synthesized and characterized by elemental analysis, single crystal X‐ray diffraction, and IR spectroscopy. Complexes 1 – 4 crystallize in the orthorhombic system with space group of Pbca and show similar 2D layers, which are interlinked to supramolecular networks by π‐π stacking interactions. Furthermore, TGA curves show that complexes 1 – 4 have good thermal stability. Solid‐state fluorescent property of complex 1 was also investigated at room temperature.     

Supramolecular Assembly of Double‐Stranded Chains,Helical Chains and Catenane‐like Layers with Flexible Ligands

Four new transition metal coordination polymers, [Co(bpndc)(phen)(H₂O)]_n ( 1 ), [Co₃(bpndc)₃(2,2′‐bpy)₂]_n·0.5n(i‐C₃H₇OH) ( 2 ), and [M(bpndc)(2,2′‐bpy)₂]_n (M = Zn, 3 ; Cu, 4 ; H₂bpndc = benzophenone ‐4,4′‐dicarboxylic acid; phen = 1,10‐phenanthroline; 2,2′‐bpy = 2,2′‐bipyridine) have been synthesized by the hydrothermal reactions and characterized by single crystal X‐ray diffraction, elemental analysis, and IR spectrum. Because of the introduction of different terminal auxiliary ligands, bpndc ligands in complexes 1 and 2 adopt different coordination modes. In complex 1 , bpndc ligands act as tridentate ligand and bridge Co^II ions into 1D double‐stranded chains; while complex 2 possesses 2D (4,4) grids, where bpndc ligands adopt tetradente and pentadentate modes. Two such grids interpenetrate to form a novel catenane‐like layer. Complexes 3 and 4 are isostructural. Bpndc ligands adopt tetradentate mode and bridge metal ions forming 1D helical chains.     

Effect of Metal Ions on the Structures of Coordination Polymers Based on Biphenyl‐2,2′,4,4′‐Tetracarboxylate

Two new coordination polymers, {[Cd₂(btc)(2,2′‐bpy)₂] · H₂O}_n ( 1 ) and [Zn₂(btc)(2,2′‐bpy)(H₂O)]_n ( 2 ) (H₄btc = biphenyl‐2,2′,4,4′‐tetracarboxylic acid, 2,2′‐bpy = 2,2′‐bipyridine), were synthesized hydrothermally under similar conditions and characterized by elemental analysis, IR spectra, TGA, and single‐crystal X‐ray diffraction analysis. In complexes 1 and 2 , the (btc)^4– ligand acts as connectors to link metal ions to give a 2D bilayer network of 1 and a 3D metal‐organic framework of 2 , respectively. The differences in the structures are induced by diverging coordination modes of the (btc)^4– ligand, which can be attributed to the difference metal ions in sizes. The results indicate that metal ions have significant effects on the formation and structures of the final complexes. Additionally, the fluorescent properties of the two complexes were also studied in the solid state at room temperature.     

New Examples of Metal Coordination Architectures of 3,3′,4,4′‐Biphenyltetracarboxylic Acid – Syntheses,Crystal Structures,and Physical Properties

Four new metal‐organic frameworks [Cu₂(2,2′‐bipy)₂(ox)(H₂O)₂]·(H₂bptc) ( 1 ), [Cu(bptc)_0.5(phen)(H₂O)]·H₂O ( 2 ), Co₂(bptc)(bmb)_1.5 ( 3 ) and [Cd₂(bptc) (bmb)]·3H₂O ( 4 ) (H₄bptc = 3,3′,4,4′‐biphenyltetracarboxylic acid, ox = oxalate, phen = 1,10‐phenanthroline, 2,2′‐bipy = 2,2′‐bipyridine and bmb = 4,4′‐bis((1H‐imidazol‐1‐yl)methyl)biphenyl), were obtained by reactions of the corresponding metal salts with H₄bptc and N‐containing auxiliary ligands and their structures were determined by single‐crystal X‐ray diffraction. The results reveal that 1 has a 0‐D structure consisting of discrete ionic entities, while 2 features a 1‐D ladder structure. Additionally, there exist π‐π stacking and intermolecular hydrogen‐bonding interactions in 1 and 2 , respectively, forming 3‐D supramolecular structures. In 3 ‐ 4 , undulating 2‐D metal‐bptc layer structures are formed with two different coordination modes of bptc carboxylate groups, respectively, which are further extended by bmb into 3‐D structures. Magnetic properties of 1 and 3 have been studied. The photoluminescence property of 4 has also been investigated. Moreover, nonlinear optical measurements showed that 4 displayed a second‐harmonic‐generation (SHG) response of 0.7 times of that for urea.     

Syntheses,crystal structures and blue emission of three zinc(II) coordination polymers with a 4,4′‐dicarboxybiphenyl sulfone ligand

Three novel zinc complexes [Zn(dbsf)(H₂O)₂] ( 1 ), [Zn(dbsf)(2,2′‐bpy)(H₂O)]·(i‐C₃H₇OH) ( 2 ) and [Zn(dbsf)(DMF)] ( 3 ) (H₂dbsf = 4,4′‐dicarboxybiphenyl sulfone, 2,2′‐bpy = 2,2′‐bipyridine, i‐C₃H₇OH = iso‐propanol, DMF = N,N‐dimethylformamide) were first obtained and characterized by single crystal X‐ray crystallography. Although the results show that all the complexes 1–3 have one‐dimensional chains formed via coordination bonds, unique three‐dimensional supramolecular structures are formed due to different coordination modes and configuration of the dbsf^2? ligand, hydrogen bonds and π–π interactions. Iso‐propanol molecules are in open channels of 2 while larger empty channels are formed in 3 . As compared with emission band of the free H₂dbsf ligand, emission peaks of the complexes 1–3 are red‐shifted, and they show blue emission, which originates from enlarging conjugation upon coordination. Copyright © 2006 John Wiley & Sons, Ltd.     

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.     

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,Crystal Structures and Fluorescent Properties of Two 2,2′‐Biquinoline‐4,4′‐dicarboxylate‐based Cadmium(II) and Cobalt(II) Complexes

Two metal‐organic coordination polymers with one‐dimensional infinite chain motif, [Cd(bqdc)(phen)₂]_n ( 1 ) and [Co(bqdc)(phen)(H₂O)₂]_n ( 2 ) (H₂bqdc = 2,2′‐biquinoline‐4,4′‐dicarboxylic acid, phen = 1,10‐phenanthroline), have been synthesized under similar solv/hydrothermal conditions and fully structural characterized by elemental analysis, IR, and single‐crystal X‐ray crystallography. Their thermal stability and photoluminescence properties were further investigated by TG‐DTA and fluorescence spectra. In both complexes, the adjacent metal ions (Cd^II for 1 and Co^II for 2 ) are linked together by dicarboxylate groups of bqdc dianions in chelating bidentate and monodentate modes, respectively, generating a zigzag chain for 1 and linear chain for 2 . The relatively higher thermal stability up to 324 °C for 1 and strong fluorescence emissions jointly suggest that they are good candidates for luminescent materials.     

Syntheses and Characterization of Three New Compounds Based on Terephthalate and 2‐(2‐Pyridin‐4‐yl‐vinyl)benzimidazole Ligands

Three new compounds based on H₂BDC and PyBImE [H₂BDC = 1,4‐benzenedicarboxylatic acid, PyBImE = 2‐(2‐pyridin‐4‐yl‐vinyl)benzimidazole], namely, [Co(PyBImE)(BDC)(H₂O)₂] ( 1 ), [Co(PyBImE)₂(HBDC)(BDC)_0.5] ( 2 ), and [(HPyBImE)⁺ · (BDC)²–_0.5 · (H₂BDC)_0.5] ( 3 ), were synthesized by hydrothermal methods and characterized by single‐crystal X‐ray diffraction. Compound 1 is a one‐dimensional chain bridged by terephthalate in a bis(monodentate) fashion. In the complex the nitrogen atom from N_BIm and the coordination water molecule complete the coordination sphere. In complex 2 , the dinuclear cobalt units are bridged by terephthalate in a bis(bidentate) fashion into a one‐dimensional chain, but different from complex 1 , the nitrogen atom from N_Py and the oxygen atom from hydrogenterephthalate complete the coordination sphere. Complex 3 is a co‐crystal with PyBImE and H₂BDC in a 1:1 ratio and the transfer of hydrogen atoms leads the complex into a salt. Interesting supramolecular structures are shown due to the hydrogen bonding as well as π ··· π interactions in the three complexes. Thermal and magnetic properties of 1 and 2 were also studied.