Hydrothermal syntheses,crystal structures,and properties of two new coordination polymers constructed from a flexible pyridinecarboxylate ligand

Two new coordination polymers with the same topological structure [Zn(L)]_2n·n(H₂O) (1) and [Co(L)]_2n·n(H₂O) (2) (H₂L = 5-(pyridin-2-ylmethoxy)-isophthalic acid) have been hydrothermally synthesized by reactions of metal salts and H₂L. Single-crystal X-ray analyses reveal that 1 and 2 are isostructural and crystallize in orthorhombic chiral P2₁2₁2 space group. These compounds feature 2-D undulated layer structures with (3,6)-connected kgd topology, which further extended into a 3-D supramolecular framework via intermolecular hydrogen bonds. In addition, the luminescent properties of 1 and 2 and the magnetic property of 2 were also investigated.     

Crystal structures and properties of four coordination polymers constructed from flexible pamoic acid

Four novel coordination polymers constructed from flexible pamoic acid, namely [Co(pam)(4,4′-bipy)]_n·nH₂O (1), [Ni(pam)(4,4′-bipy)(H₂O)₂]_n·2nCH₃CN (2), [Cd(pam)(py)₂]_n·npy (3) and [Mn₂(pam)₂(py)₆(H₂O)₂]_n·2npy (4), (H₂pam = pamoic acid, 4,4′-bipy = 4,4′-bipyridine, py = pyridine), have been synthesized and characterized by elemental analysis, infrared spectra and X-ray crystallography. Complex 1 is a 2-D coordination polymer constructed from chelating bis-bidentate pam and 4,4′-bipyridine bridging ligands. Complex 2 is a 2-D coordination polymer assembled by bis-monodentate pam and 4,4′-bipyridine, where acetonitrile is filled in the rectangle channels. Both 2-D coordination polymers display undulated (4,4) grid layers as sql topology. Complex 3 displays a 1-D polymeric chain using chelating bis-bidentate pam as bridging ligand. Complex 4 exhibits an interesting bis-monodentate pam-Mn(II) 1-D polymeric chain, in which exist two-type six-coordinated manganese centers. Mn(1) is bound to four pyridine ligands, whereas Mn(2) is combined to two pyridine and two H₂O molecules. Their thermal stabilities have been investigated. Cadmium complex 3 displays strong green luminescence with emission maximum at 543 nm.     

Syntheses,crystal structures,and luminescence of carboxylato-bridged coordination compounds

Two 2-D metal carboxylate coordination compounds [Tb(pydc)(ox)_1/2(H₂O)₂] (1) and [Cd(pydc)(me)(H₂O)]₂ · H₂O (2) (pyridine-2,5-dicarboxylic acid = pydc, oxalic acid = ox, me = methanol) have been synthesized under hydrothermal conditions. Carboxylates are building blocks in the formation of zigzag chain and cockle stair-like chain structures for 1 and 2, respectively. Both the compounds have been structurally determined by single-crystal X-ray diffraction, and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and fluorescence spectra.     

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。     

Novel coordination polymers with ferrocene-containing dicarboxylate ligand: Syntheses, crystal structures and properties

A new ferrocene-containing dicarboxylate ligand, L = 5-ferrocene-1,3-benzenedicarboxylic acid, has been prepared. Self-assembly of L, M(II) salts (M = Co and Zn) and chelating ligands dpa or phen (dpa = 2,2′-dipyridylamine and phen = 1,10-phen) gave rise to four new coordination polymers {[Co(L)(dpa)] · 2MeOH}_n (1), {[Zn(L)(dpa)] · 2MeOH}_n (2), {[Co(L)(phen)(H₂O)] · MeOH} (3), [Zn(L)(phen)(H₂O)] · MeOH (4). The isostructural complexes 1 and 2 possess 1D helical chain structures with 2₁ screw axes along the b-direction, and the right- and left-handed helical chains are alternate arrayed into 2D layer structures through hydrogen-bonding interactions; while isostructural complexes 3 and 4 are 1D linear chain structures with phen and ferrocene groups of L as pendants hanging on the different sides of the main chain. A structural comparison of complexes 1–4 demonstrated that the characteristics of subsidiary ligands and slight difference in coordination models of L play very important role in the construction of the complexes. In addition, the redox properties of complexes 1–4, as well as the magnetic properties of complexes 1 and 3 are also investigated.     

Syntheses, structures and properties of five copper coordination polymers constructed by the triazole ligand

Reactions of different metal salts with 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-abpt) gave rise to five new complexes, namely [Cu₄(CN)₄(3-abpt)₂]_n (1), [CuBr(3-abpt)]_n (2), [CuI(3-abpt)]_n (3), [Cu₃I₃(3-abpt)]_n (4) and [Cu(3-abpt)(SO₄)(H₂O)]_n (5). Compounds 1, 3, 4 and 5 are all 2D structures. Compound 1 is a double-layered polymer with an uncommon 3-nodal 3-connected (10³)(10².4)₄ network, 3 shows a 2D square layered structure, 4 is also a double-layered polymer with 2-nodal 4-connected (3.4.5.6².7)₂(3.4².5².7) network and 5 is a 2D structure which is ultimately stacked with an ABAB repeat pattern. Compound 2 is a 1D coordination polymer which exhibits a ladder-like network. The photoluminescence of 1-2 has also been investigated. The long emission lifetimes of 1-2 could be assigned to metal-to-ligand charge transfer triple excited states [MLCT].     

Transition metal coordination complexes based on V-shaped bis-triazole ligand: syntheses,structures, and properties

Hydrothermal reactions of 1,3-bis(1,2,4-triazol-1-yl)benzene (btb) and M(NO₃)₂ (M = Co²⁺ (1), Cu²⁺ (2)) afforded two new coordination polymers, [Co(btb)₂(NO₃)(H₂O)]_n·NO₃·H₂O (1) and [Cu(btb)₂(NO₃)₂]_n (2), respectively. Single-crystal X-ray diffraction reveals that 1 crystallizes in the space group P2₁/m and 2 crystallizes in the space group Pī, both showing a double-stranded chain structure. The 1-D chains are interconnected via π?π interactions to lead to 2-D ladder-like supramolecular architectures. In addition, magnetic behavior and thermal stability of 1 and 2 have been investigated. For 1, weak antiferromagnetic interactions are observed at low temperature, and the data obey the Curie–Weiss law χ_M = C/(T?θ), with C = 3.22 cm³·mol^?1·K and θ = ?10.39 K. For 2, the decrease of the χT vs. T curve at low temperature is the result of intermolecular antiferromagnetic magnetic interactions.     

Syntheses,structures, and properties of four coordination polymers based on 2,7-di(pyridin-4-yl)-9H-fluoren-9-one

Four coordination polymers (CPs), [Cd(2,7-dpfo)₂(NO₃)₂(CH₃OH)]_n (1) , [Zn(2,7-dpfo)(NO₃)(CH₃COO)]_n (2) , [Co(2,7-dpfo)₂(H₂L)]_n (3) , and [Ni(2,7-dpfo)₂(H₂L)]_n (4) (where 2,7-dpfo is 2,7-di(pyridin-4-yl)-9H-fluoren-9-one and H₄L is 1,1′:4′,1′′-terphenyl-4,2′,5′,4′′-tetracarboxylic acid), were synthesized and structurally characterized. Compounds 1 – 4 were determined by elemental analyses, single crystal X-ray diffraction analyses, powder X-ray diffraction, infrared spectroscopy, and thermogravimetric analyses. Compound 1 displays a one-dimensional (1D) zigzag chain structure, while compound 2 possesses a 1D ladder chain structure. Compounds 3 and 4 are isostructural and consist of 1D chains. The solid-state luminescent properties of 1 and 2 and the magnetic properties of 3 and 4 were also investigated.     

Syntheses,crystal structures,and magnetic properties of five new coordination compounds bearing ferrocenedicarboxylate ligands

Five new coordination compounds, {[Mn(L)(CH₃OH)₂] · CH₃OH · H₂O} _n (1), {[Cd(L)(DMF)₂(H₂O)] · H₂O} _n (2), {[Co(L)(CH₃OH)₄] · CH₃OH}₂ (3), {[Cd(L)(phen)(CH₃OH)] · CH₃OH} _n (4), and {[Mn(L)(phen)(H₂O)] · CH₃OH} _n (5) (L = 5-ferrocene-1,3-benzenedicarboxylic acid, phen = 1,10-phenanthroline) were obtained from different metal salts and L with or without 1,10-phen under mild conditions. Complex 1 is a 1-D ladder-like chain composed of 8-membered rings A and 16-membered rings B, which arrange alternately. Complex 2 is an infinite linear chain, further bridged to form a parallel double chain through different hydrogen-bond interactions. Complex 3 is a discrete dinuclear structure, while 4 is a neutral 1-D infinite zigzag coordination chain. Complex 5 is a 1-D linear chain with phen and ferrocene groups of L as pendants hanging on the different sides of the main chain. Variable temperature magnetic susceptibilities of 1 were measured and weak antiferromagnetic exchange interactions between the neighboring Mn(II) ions were found with J = ?0.95 cm^?1.     

Syntheses,crystal structures,and properties of four new coordination compounds of transition metals and imidazoledicarboxylic acid derivatives

Four new transition metal coordination complexes, [Cd(H₂pimdc)₂(H₂O)₂]?·?4H₂O (1), [Zn(H₂pimdc)₂(H₂O)₂]₂?·?7H₂O (2), and [M(H₂pimdc)₂] (M?=?Cu (3) or Ni (4), H₂pimdc^??=?2-propyl-4,5-imidazoledicarboxylate), have been prepared by conventional synthesis and characterized by elemental analyses, IR, TG, and single-crystal X-ray diffraction. H₂pimdc^? is a bidentate chelating ligand in 1 and 2, leading to 3-D supramolecular structures through hydrogen bonds. However, H₂pimdc^? is a tridentate chelating-bridge ligand in 3 and 4, which exhibit 2-D layer structures. Thermal properties and photoluminescence spectra of 1–4 were measured.     

Syntheses,structures and luminescent properties of four d-metal coordination polymers based on the 2,4,5-tri(4-pyridyl)-imidazole ligand

Four d¹⁰-metal coordination polymers based on the 2,4,5-tri(4-pyridyl)-imidazole ligand (Htpim), {[Zn₂(Htpim)₄Cl₄] · 8H₂O}_n (1), {[Cd(tpim)₂(H₂O)₂] · 4CH₃OH}_n (2), {[Cu₂(Htpim)(PPh₃)₂I₂] · CH₃CN}_n (3) and {[Ag(Htpim)](NO₃) · CH₂Cl₂}_n (4), have been synthesized and characterized by elemental analyses, IR, thermogravimetric and X-ray structural analyses. Both complexes 1 and 2 show one dimensional ribbon-like structures. Via intermolecular hydrogen bonds, a 2D supramolecular network and 3D framework are formed for 1 and 2, respectively. Complex 3 shows a 1D zigzag chain with a CuI₂Cu rhomboid dimer. Complex 4 shows a 1D ladder-like polymer with two different metallacycles. The luminescent properties of all the complexes have been studied in the solid state.     

Syntheses, crystal structures and properties of six coordination compounds with flexible dps ligand

Six new compounds: [M(dps)(dca)₂]_∞ (1, M = Cd; 2, M = Fe), [Cu(dps)(dca)₂(CH₃OH)₂]_∞ (3), [M(dps)₂(SCN)₂(H₂O)₂]_∞ (4, M = Cd; 5, M = Fe), [Cu(dps)₄(SCN)₂]_∞ (6), (dps = 4,4′-dipyridyl sulfide, dca = dicyanamide) were synthesized, characterized by FT-IR, element analysis and TG. Their structures were determined by single crystal X-ray diffraction. According to the structure analysis, compounds 1 and 2 are three-dimensional microporous frameworks constructed by Cu-dps-Cu and Cu-dca-Cu bridges; compound 3 shows a zigzag chain constructed by a Cu-dps-Cu bridge; compounds 4 and 5 show double-stranded chains constructed by a Cu-(dps)₂-Cu bridge while thiocyanate anions act as terminal groups; compound 6 is a mononuclear compound. Moreover, compound 1 shows visible yellow luminescence under UV light irradiation and such phenomenon is mainly attributed to inter-ligand transitions.     

Syntheses,crystal structures and properties of four metal coordination complexes constructed from aromatic carboxylate and benzimidazole-based ligands

Transition Metal Chemistry - Four metal–organic coordination complexes, namely {[Zn(SIP)(mbi)2]·(Hmbi)·(H2O)2}n (1), {[Cd3(SIP)2(bbhb)3(H2O)4]·(H2O)2}n (2),...     

The architectures of 1D coordination polymers with the versatile 7-chloroquinoline-4-alanine ligand mediated by anions: Syntheses,structures and luminescent properties

Three new coordination polymers, [Cd(cqaH)(cqa)Cl]_n (1), [Cd(cqaH)(cqa)Br]_n (2) and {[Cd₂(cqa)₄] · 3H₂O}_n (3) (Hcqa = 7-chloroquinolin-4-alanine, cqaH = the Hcqa ligand, where the proton is transferred from the acid group to the imine group) have been prepared under hydrothermal conditions and characterized by X-ray structural analyses. Both complexes 1 and 2 possess 1D ribbon-like chains, and complex 3 features a 1D double-stranded chain. Various coordination fashions and supramolecular networks are observed in complexes 1–3 due to the versatile coordination modes of the ligand and the cooperative effect from anions in the assemblies. In addition, the luminescent properties for all compounds have been investigated in the solid state.     

Syntheses, structures and luminescent properties of a series of 3D lanthanide coordination polymers with tripodal semirigid ligand

Reactions of the tripodal bridging ligand 5-(4-carboxy-phenoxy)-isophthalic acid (abbreviated as H₃cpia) with lanthanide salts lead to the formation of a family of different coordination polymers, that is, [Ln(cpia)(H₂O)₂]_n·nH₂O (Ln=Ce (1), Pr (2), Nd (3), Sm (4), Eu (5), Gd (6), Dy (7), Er (8), Tm (9) and Y (10)) in the presence of formic acid or diethylamine, which are characterized by elemental analysis, IR spectrum, thermogravimetric analysis (TGA), XRPD spectrum and single-crystal X-ray diffraction. Compounds 1-10 are isostructural and exhibit three-dimensional microporous frameworks. Furthermore, the photoluminescent properties of 4, 5 and 7 have been studied in detail.     

Syntheses and characterizations of four metal coordination polymers constructed by the pyridine-3,5-dicarboxylate ligand

A series of metal-organic frameworks, namely [Ni(PDB)(H₂O)]_n (1), [Pb(PDB)(H₂O)] · (H₂O) (2), [Co₂(PDB)₂(bpy)₂(H₂O)₄] · 4H₂O (3) and [Co₂(PDB)₂(phen)₂]_n (4) (H₂PDB = pyridine-3,5-dicarboxylic acid, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline), have been synthesized based on pyridine-3,5-dicarboxylate acid and two neutral chelate ligands, with different metal ions such as Ni^II, Co^II and Pb^II, under hydrothermal conditions. The framework structures of these polymeric complexes have been determined by the X-ray single crystal diffraction technique. In the four complexes, the pyridine-3,5-dicarboxylate acid ligand exhibits diverse coordination modes, which play an important role in the construction of metal-organic frameworks. The thermal analyses of these four complexes have been measured and discussed. In addition, complex 2 shows strong phosphorescent emission at room temperature and the magnetic measurement of the polymer of 4 reveals a typical antiferromagnetic exchange.     

Syntheses, structures, and electrochemical properties of four complexes based on 4-ferrocenylbutyrate ligand

Four ferrocenyl complexes with the formulas {[Mn(η²-OOC(CH₂)₃Fc)₂(bbbm)]·CH₃OH}_n (1), {[Co(OOC(CH₂)₃Fc)(η²-OOC(CH₂)₃Fc)(bbbm)]·CH₃OH}_n (2), {[Ni(OOC(CH₂)₃Fc)₂(bbbm)(CH₃OH)₂]·2CH₃OH}_n (3) and [Pb₆(μ₂-OOC(CH₂)₃Fc)₂(μ₃-OOC(CH₂)₃Fc)₂(μ₂-η²-OOC(CH₂)₃Fc)₂(η²-OOC(CH₂)₃Fc)₂(μ₄-O)₂] (4) (Fc = (η⁵-C₅H₅)Fe(η⁵-C₅H₄), bbbm = 1,1-(1,4-butanediyl)bis-1H-benzimidazole) have been synthesized and characterized by single crystal X-ray diffraction. Owing to the different conformations of the bbbm units in complexes 1 (or 2) and 3, complexes 1 and 2 possess 1D helical chain structure with 2₁ screw axes along the b-direction, while complex 3 shows a 1D linear chain structure with ferrocenylbutyrate groups hanging on the chain. Complex 4 is a hexanuclear complex and exhibits a nano-scale wheel-like framework with six Pb(II) ions as a core and eight 4-ferrocenylbutyrate ligands as branches. The cyclic voltammetric studies show that the formal potentials of the four complexes are close to the free ferrocenylbutyrate ligand, which indicates that the coordination of the metal ions to the ferrocenyl ligand does not have significant effects on the redox potential of the ferrocenylbutyrate ligand. Further investigations suggest that the redox processes of the ferrocenylbutyrate ligand and complexes 1-4 are all chemically quasi-reversible processes and controlled by diffusion.     

Syntheses,structures, luminescent and magnetic properties of two coordination polymers based on a fl exible multidentate carboxylate ligand

Two coordination polymers,{[Cu_3(tci)_2(DMAc)_3]-6DMAc 2H_2O}_n(1) and {[Cu_3(tci)_2(tpt)_2(H_2O)_2].2DMAc-2H_2O}_n(2)(H_3tci = tris(2-carboxyethyI)isocyanurate,tpt = 2,4,6-tris(4-pyridyl)-l,3,5-triazine,DMAc = N,/V-dimethylacetamide),have been constructed under solvothermal conditions.Both polymers were structurally characterized by single crystal X-ray diffraction,elemental analyses,IR spectra,thermogravimetric(TG) analyses and powder X-ray diffraction(RXPD).1 shows a(3,4)-connected 2D layer structure comprising Cu_2(CO_2)4 paddle-wheel units,which are further bridged by C-H…O interactions to give a 3D supramolecular network.The introduction of tpt produces different framework for 2 that comprises a dinuclear and a mononuclear Cu(Ⅱ) building units,which are further bridged together by tci~(3-) and tpt ligands to give a 4-connected 2D topological net.Adjacent 2D layers are packed together via C-H…O interactions and π…π stacking interactions to form a 3D supramolecular structure.In addition,the luminescent properties and the solid-state UV-vis spectra of 1 and 2 were explored.Furthermore,antiferromagnetic exchange interactions were unveiled in the Cu_2(COO)_4 units of 1.     

Syntheses, structures and photoluminescence of a series of coordination frameworks based on dicarboxylate anion and bis(imidazole) ligand

In this article, ten new coordination frameworks, namely, [Ni(H₂O)₆]·(L3) (1), [Zn(L3)(H₂O)₃] (2), [Cd(L3)(H₂O)₃]·5.25H₂O (3), [Ag(L1)(H₂O)]·0.5(L3) (4), [Ni(L3)(L1)] (5), [Zn(L3)(L1)_0.5]·H₂O (6), [Cd(L3)(L1)_0.5(H₂O)] (7), [CoCl(L3)_0.5(L1)_0.5] (8), [ZnCl(L3)_0.5(L2)_0.5] (9), and [CoCl(L3)_0.5(L2)_0.5] (10), where L1 = 1,1′-(1,4)-butanediyl)bis(imidazole), L2 = 1,1′-(1,4-butanediyl)bis(2-ethylbenzimidazole) and H₂L3 = 3,3′-(p-xylylenediamino)bis(benzoic acid), have been synthesized by varying the metal centers and nitrogen-containing secondary ligands. These structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses and IR spectra. In 1, the L3 anion is not coordinated to the Ni(II) center as a free ligand. The Ni(II) ion is coordinated by water molecules to form the cationic [Ni(H₂O)₆]²⁺ complex. The hydrogen bonds between L3 anions and [Ni(H₂O)₆]²⁺ cations result in a three-dimensional (3D) supramolecular structure of 1. In compounds 2 and 3, the metal centers are linked by the organic L3 anions to generate 1D infinite chain structures, respectively. The hydrogen bonds between carboxylate oxygen atoms and water molecules lead the structures of 2 and 3 to form 3D supramolecular structures. In 4, the L3 anion is not coordinated to the Ag(I) center, while the L1 ligands bridge adjacent Ag(I) centers to give 1D Ag-L1 chains. The hydrogen bonds among neighboring L3 anions form infinite 2D honeycomb-like layers, in the middle of which there exist large windows. Then, 1D Ag-L1 chains thread in the large windows of the 2D layer network, giving a 3D polythreaded structure. Considering the hydrogen bonds between the water molecules and L3 anions, the structure is further linked into a 3D supramolecular structure. Compounds 5 and 7 were synthesized through their parent compounds 1 and 3, respectively, while 6 and 9 were obtained by their parent compound 2. In 5, the L3 anions and L1 ligands connect the Ni(II) atoms to give a 3D 3-fold interpenetrating dimondoid topology. Compound 6 exhibits a 3D three-fold interpenetrating α-Po network structure formed by L1 ligands connecting Zn-L3 sheets, while compound 7 shows a 2D (4,4) network topology with the L1 ligands connecting the Cd-L3 double chains. In compound 8, the L1 ligands linked Co-L3 chains into a 2D layer structure. Two mutual 2D layers interpenetrated in an inclined mode to generate a unique 3D architecture of 8. Compounds 9 and 10 display the same 2D layer structures with (4,4) network topologies. The effects of the N-containing ligands and the metal ions on the structures of the complexes 1-10 were discussed. In addition, the luminescent properties of compounds 2-4, 6, 7 and 9 were also investigated.