Two Metal-organic Coordination Polymers with Rigid Bis(triazole) Ligand: Assembly,Structures, and Fluorescence Properties

Two new coordination polymers containing rigid bis(triazole), namely, [Ni(btb)_(0.5)(nph)(H_2O)]_n(1) and [Zn(btb)(SO_4)]_n(2)(btb = 4,4?-bis(1,2,4-triazolyl-1-yl)-biphenyl, H_2nph = 3-nitrophthalic acid) have been synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. Complex 1 shows a 3D trinodal(3,4,4)-connected sqc69 topology. Complex 2 presents a 2D uninodal 4-connected sql network, which is further packed into a 3D supramolecular framework by C–H···O hydrogen bonds. Thermal stabilities and fluorescence properties of two complexes have been discussed in detail.     

Spacer Length Effects on the Structure of Cd(Ⅱ) Coordination Polymers with Flexible Bis(thiabendazolyl)(1) Alkane and 1,2,4,5-Benzenetetracarboxylte Ligands

The hydrothermal reactions of Cd(OAc)2·2H2O with 1,2,4,5-benzenetetracarboxylic acid(H4bta) and 1,4-bis(thiabendazolyl)butane(L1) or 1,6-bis(thiabendazolyl)hexane(L2) afforded two coordination polymers [Cd2(L1)(bta)·2H2O]n(1) and [Cd2(L2)2(H2bta)2]n(2). Complex 1 holds a rare 3D binodal(4,6)-connected framework with fsh topology. Complex 2 features an infinite meandering chain structure, which is further extended via O–H···O hydrogen bonding into a 3D supramolecular network. The thermal and fluorescence proprieties of the two complexes were investigated.     

A Three-dimensional Self-penetrating Co(Ⅱ) Coordination Polymer Containing a 2D → 3D Parallelly Polycatenated Subnet

Hydrothermal assembly of Co~(2+) ion, a bis-imidazole ligand BIMB(BIMB = 1,4-bis(imidazol-1-yl)benzene) and a rigid bidentate linker 2,6-naphthalenedicarboxylic acid(H_2ndc), yields a novel three-dimensional(3D) self-penetrating coordination polymer {[Co(BIMB)(ndc)]·H_2O}_n(1). Complex 1 exhibits {6~5.8} topology and contains a 2D → 3D parallel polycatenated substructure. In addition, solid-state UV-vis absorption spectra of 1 were also investigated.     

Syntheses,Structures and Characteristics of Two New Cu(Ⅱ) Coordination Polymers Based on 4-tert-butyl-phthalate and Different Bis(1,2,4-triazol-1-yl) Co-Ligands

Two new Cu(II) coordination polymers, [Cu2(tbph)2(btb)2]n(1) and {[Cu2(tbph)2-(bth)2]·H2O}n(2),(H2tbph = 4-tert-butyl-phthalic acid, btb = 1,4-bis(1,2,4-triazol-1- yl)butane, bth = 1,6-bis(1,2,4-triazol-1-yl)hexane), have been synthesized and characterized by elemental analysis, FT-IR and X-ray single-crystal diffraction. Complex 1 has a 2D sql layer. Complex 2 shows a(3,4)-connected 2D sheet with a(4.64.8)(4.82) topology. The thermal behavior of the two corresponding complexes has briefly been investigated.     

Synthesis,Structure, and Luminescent Properties of Two Complexes Based on Flexible Phenylenediacetate Ligand

Two new Zn(Ⅱ) and Cd(Ⅱ) coordination complexes, [Zn(ppda)(idz)]_n(1) and [Cd(mpda)(mbib)]_n(2)(H2 ppda = 1,4-phenylenediacetic acid, H_2 mpda = 1,3-phenylenediacetic acid, idz = imidazole, mbib = 1,3-bis(imidazol-1-ylmethyl)benzene), have been synthesized by using Zn(Ⅱ)/Cd(Ⅱ) salt and phenylenediacetic acid in the presence of different imidazole ligands under hydrothermal conditions, and characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography and thermogravimetric analysis. Complex 1 crystallizes in orthorhombic system, Iba2 space group. The carboxylic acid ligands form a 2 D helical layer with Zn(Ⅱ) ions, and such layers are expanded into a 3 D network structure by the force of C–H×××π. Complex 2 crystallizes in monoclinic system, P2_1/n space group. Complex 2 shows a 3 D framework with two Cd(Ⅱ) ions as nodes of a dual-core unit, which can be considered to be 6-connected net and regarded as a rare(4~4,5~(10),7) topology network with self-interlacing. The structural diversities indicate that rigid and flexible imidazole ligands play dominating roles in modulating the formation of structures of these crystalline materials. Moreover, the luminescent properties of two complexes are investigated in solid state.     

Two Zn~Ⅱ Coordination Polymers with 2,2?-Oxybis(benzoic acid) and Different N,N?-Donor ligands

Two new Zn~Ⅱ coordination polymers [Zn(oba)(4,4?-bipy)]n(1) and [Zn(oba)-(bpe)_(1/2)(H_2O)]_n(2)(H_2oba = 2,2?-oxybis(benzoic acid), 4,4?-bipy = 4,4?-bipyridine, bpe = 1,2-bis(4-pyridyl)ethylene) were synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, IR spectroscopy and elemental analysis. Complex 1 shows a 3D metal-organic framework with a uninodal 4-connected 65.8 dmp network. Complex 2 features 1D ladder-shaped chains, which are further connected into a 2D stair-step network through intermolecular O–H···O hydrogen bonds.     

Syntheses,Crystal Structures and Luminescent Properties of Lead(Ⅱ) and Cadmium(Ⅱ) Coordination Polymers Constructed from Biphenyl-2,5,3′-tricarboxylate

Two coordination polymers, namely [Pb(Hbtc)(phen)]n(1) and {[Cd3(btc)2(H2O)4]·2H2O}n(2, H3btc = biphenyl-2,5,3'-tricarboxylic acid, phen = 1,10-phenanthroline), were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a zigzag chain 1D coordination network, which is further extended into a 3D supramolecular architecture via O–H···O hydrogen bonds and π-π packing interactions. Compound 2 features a 3D open framework based on a tricadmium(II) subunit, generating a trinodal 4,4,6-connected net with the 4,4,6T24 topology defined by the point symbol of(44·62)3(46·69)2. Thermal stability and luminescent properties of both compounds were studied and discussed.     

Interpenetration of Three 2D In-MOFs with(6,3) Topology:Syntheses,Structures and Fluorescent Properties

Three indium metal-organic frameworks(In-MOFs), [In(BTB)(2,2?-bipy)]·NMP(1), [In(BTB)(2,2?-bipy)]·NMP·2H_2O(2), and [In(BTB)(NMP)]·0.5NMP(3), have been constructed by the solvothermal reaction of In(NO_3)3·5H_2O and 1,3,5-benzenetribenzoic acid(H3BTB) in similar reaction conditions, and characterized by single-crystal X-ray crystallography, power X-ray diffraction(PXRD), infrared spectroscopy(IR), elemental analysis(EA) and thermogravimetry analysis(TGA). Complex 1 bears a two-dimensional(2D) layered structure of 6,3-connected hcb net topology, and complexes 2 and 3 have 2-fold interpenetrating structures based on 6,3-connected layer, which display the same net topologies with the C_3-symmetric H_3B TB ligands as 3-connected linkers and the In(ⅡI) ions as 6-connected nodes. Moreover, the fluorescent properties of 1~3 have also been studied.     

Hydrothermal Syntheses,Crystal Structures,and Characterization of Two Zinc(Ⅱ) Complexes Containing Flexible Bis(benzimidazole) Ligands

Two zinc(Ⅱ) complexes, namely, [Zn(L_1)Cl_2]_2(1) and {[Zn(L_2)(tbta)]·3H_2O}n(2)(L_1 = 1,3-bis(2-methylbenzimidazol-1-ylmethyl)benzene, H2 tbta = tetrabromoterephthalic acid, L2_ = 1,3-bis(2-methylbenzimidazol-1-yl)-2-propanol), have been successfully obtained under hydrothermal conditions. Complex 1 displays a binuclear structure which is further extended into a 1D supramolecular chain through π-π stacking. Complex 2 features a 2D(4,4) network based on a L2/tbta2- double linker. The thermal stability, fluorescence properties and catalytic activities of two complexes for the degradation of methyl orange in a Fenton-like process were discussed.     

Water-induced reversible dissolution/reorganization transformations of Cu(Ⅱ)-K(I) heterometallic coordination polymers

Three new heterometallic coordination compounds, namely, [KCu(I3)(L)2(H2O)2]n(1), [KCu(I3)(L)2(H2O)]n(2) and [CuK4(I3)2(L′)4]n(3), were prepared and characterized(HL=5-methylpyrazine-2-carboxylic acid, HL′=p-tolylacetic acid). Structural studies revealed that 1 and 2 exhibit 3D frameworks with rectangular channels occupied by triiodide ions. Both compounds can be symbolized as a 5-connected net with pcu topology. In compound 3, a one-dimensional polyhedral chain is connected by hexanuclear mask like clusters [Cu2K4O8]. These chains are further linked each other via rare(1,1,3,3)-triiodide ion-bridging units to generate a 3D(4,5,6)-connected net with the point symbol of {12}2{4·122}4{46}{48·62}4{49·66}4. It is noteworthy that water-induced reversible dissolution/reorganization processes occur between 1/2 and [Cu(L)2(H2O)]n·3nH2O. The thermal and photoluminescence properties of compounds 1, 2, and 3 were investigated as well.     

Two Interpenetrated and Polycatenated Zn(Ⅱ) Coordination Polymers: Syntheses,Structures and Luminescent Properties

Two fascinating Zn(II)entangled coordination polymers,[Zn(eoba)(bbi)]_n·nH_2O(1)and[Zn(boba)(bbi)_(1/2)]_n(2),(bbi=1,1?-(1,4-butanediyl)-bis(imidazole),H_2eoba=4,4?-(ethane-1,2-diyldioxy)-dibenzoic acid,H_2boba=4,4?-(butane-1,4-diyldioxy)-dibenzoic acid),were obtained by hydrothermal technology and characterized by elemental analysis,infrared spectrum,thermogravimetric analysis and single-crystal X-ray diffraction.1 is a rare 2D→3D example with a 3-fold parallel interpenetration and polycatenaned architecture.2 features a scarce2D→2D example with a 3-fold parallel interpenetrating network which possesses polyrotaxane and polycatenane characters.Moreover,the luminescent properties of 1 and 2 have been discussed.     

Two New Mn(Ⅱ)/Co(Ⅱ) Complexes Assembled by 2,5-Dihydroxy-1,4-benzenedicarboxylic Acid and Phenanthroline or Derivative

Two new complexes [Mn(DHTA)(PLQ)]n(1) and{[Co2(DHTA)(phen)2(H2 O)6]· DHTA}n(2)(H2 DHTA = 2,5-dihydroxy-1,4-benzenedicarboxylic acid, PLQ = 1,10-phenanthroline-5,6-quinone, phen = 1,10-phenanthroline) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, fluorescence spectrum, single-crystal and power X-ray diffraction. Complex 1 exhibits a two-dimensional(2 D) network, which was stabilized through O–H···O hydrogen bonding interactions. Complex 2 shows a zero-dimensional structure, which was further extended into a three-dimensional supramolecular structure through O–H···O hydrogen bonds and π-π interactions.     

Organic Carboxylate Ligand Tuned Topological Variations in Three Zn(Ⅱ) Coordination Polymers: Syntheses,Crystal Structures and Photoluminescent Properties

Three new Zn(Ⅱ) coordination polymers, namely [Zn_2(suc)_2(bib)_2]_n·nH_2 O(1), [Zn(glu)(bib)]_n·4 nH_2 O(2), and [Zn(adp)(bib)]n(3)(bib = 1,4-bis(N-imidazolyl)butane, H_2 suc = succinic acid, H_2 glu = glutaric acid, H_2 adp = adipic acid) have been hydrothermally synthesized and structurally characterized. Compound 1 features a 3D framework with 4-connected hxg-d topological network, compound 2 is comprised of 2D 4~4-sql-type sheets, and the adjacent 2D sheets are further packed into a 3D supramolecular architecture via intermolecular hydrogenbonding interactions, and compound 3 is a 3D framework with 4-fold interpenetrating dia topology. The structural comparison of these three compounds demonstrates that the topological variations can be well controlled by employing aliphatic dicarboxylate ligands with different spacer lengths. Moreover, the thermal stabilities and photoluminescent properties of them were also studied in detail.     

Controlled Self-assembly of Two Coordination Polymers via subtly Varying Bis（2-methyl imidazole） Ligands： from 3-Connected （6,3） Net to 4-Connected sql Net①

Two coordination polymers constructed from 3,4-thiophenedicarboxylic acid and bis(2-methyl imidazole) ligands, namely, {[Cd2(tdc)2(bip)2]·7H2O}n(1) and [Cd(tdc)(bib)]n(2)(H2tdc = 3,4-thiophenedicarboxylic acid, bip = 1,3-bis-(imidazol-2-methyl)propane and bib = 1,4-bis(imidazol-2-methyl)butane), have been synthesized and structurally characterized by single-crystal X-ray diffraction. Structural analyses reveal that 1 exhibits a two-dimensional(2D) layered network with 3-connected(6,3) topology, which is further connected into a threedimensional(3D) supramolecular structure by intermolecular hydrogen bonds. However, 2 features a 2D network which can be rationalized as a 4-connected sql net. The results indicate the subtle difference of auxiliary bis(imidazol-2-methyl) ligands may lead to diverse architectures. Moreover, they exhibit luminescence emission in the solid state at room temperature.     

Two Novel Coordination Polymers with(6,3) Topology Constructed by an Imidazole-containing Isophthalic Ligand:Syntheses,Structures and Luminescence Properties

Two novel coordination polymers,[Zn(ImNIPA)(DMSO)]n(1)and[Cd(ImNIPA)(DMSO)]n(2)(H2ImNIPA=5-(6-(1H-imidazol-1-yl)-1,3-dioxo-1H-benzo[de]iso-quinolin-2(3H)-yl)isophthalic acid,DMSO=dimethylsulfoxide),were prepared under solvothermal conditions through the reactions of Zn^2+/Cd^2+ and a new imidazole-containing isophthalic ligand H2ImNIPA.The compounds were fully characterized by elemental analysis,FT-IR spectroscopy,powder X-ray diffraction analysis and X-ray single-crystal diffraction analysis.Both 1 and 2 are two-dimensional(2D)coordination layers via the combination of 3-connected metal nodes and ImNIPA^2- linker,featuring(6,3)honeycomb-type topology.In addition,the 2D layers in the two compounds are further extended into 3D supramolecular frameworks via π-π stacking interactions.Finally,the thermal-stability and solid-state luminescence properties of them were also investigated.     

Structures and Photoluminescent Properties of Two Complexes Based on Dipyrido[3,2-a:2?,3?-c]phenazine and 2,4?-Biphenyldicarboxylic Acid

ABSTRAC Two new complexes [Cd(2,4?-bpdc)(DPPZ)]_(2n)·n H_2O(1) and [Zn(2,4?-Hbpdc)_2(DPPZ)]· H_2O(DPPZ = dipyrido[3,2-a:2?,3?-c]phenazine, 2,4?-H_2bpdc = 2,4?-biphenyldicarboxylic acid) have been hydrothermally synthesized. The structure of complex 1 was determined by single-crystal X-ray diffraction diffraction and further characterized by elemental analysis, IR spectrum, powder X-ray diffraction(XRD) and single-crystal X-ray diffraction. Complex 1 has 1D chains, which are further connected by π-π stacking interactions of neighbouring chains, generating a steady 3D supramolecular structure. Complex 2 shows the isolated mononuclear units, which are further extended to a 2D supramolecular layered structure through π-π stacking interactions and hydrogen bonds. Furthermore, complexes 1 and 2 exhibit green photoluminescent properties at room temperature.     

A series of novel Zn(Ⅱ) and Mn(Ⅱ) metal-organic frameworks constructed by 2,4-bis-oxyacetate-benzoic acid: syntheses,structures and photoluminescence

A new carboxylic acid ligand, 2,4-bis-oxyacetate-benzoic acid(H3BOABA), was designed and introduced to construct novel metal-organic framework materials. [Zn Na(BOABA)(phen)(H2O)]·H2O(1), Zn Na(BOABA)(2), Mn3(BOABA)2(phen)2(3), [Mn2(BOABA)(OH)]·(H2O)2(4)(CCDC: 885138, 885137, 894225, 883094) were hydrothermally synthesized and characterized by elemental analysis, IR spectra and thermal gravimetric analyses. Crystal structures of the complexes were determined by single crystal X-ray diffraction method. Complex 1 is a one dimensional double edges non-interpenetrated framework decorated by the phen ligands on the surface. Complex 2 is an unique three dimensional open framework, consisting of Zn(II) and Na(I). Complex 3 is an unique double edges one dimensional MOF containing a [Mn3(BOABA)2(phen)2]n non-interpenetrated structure. Complex 4 is a two dimensional plane structure containing two Mn atoms in the same coordination environment. The interaction between four complexes and DNA were studied by Et Br fluorescence probe. Meanwhile, photoluminescence studies revealed that these four complexes display strong fluorescent emission bands in the solid state at room temperature.     

Syntheses,Structures and Photoluminescent Properties of Cd(Ⅱ) Polymeric Complexes Based on 5-Aminoisophthalic Acid and Bipyridine Co-ligands

Two novel complexes, namely {[Cd(AIP)(4,4?-bpy)]·1.3DMF}n(1) and [Cd(AIP)(2,2?- bpy)]n(2), have been synthesized through solvothermal reaction(H2AIP = 5-aminoisophthalic acid, 2,2?-bpy = 2,2?-bipyridine, 4,4?-bpy = 4,4?-bipyridine, and DMF = N,N?-dimethylformamide) and structurally determined by single-crystal X-ray diffraction. Complex 1 shows a three-dimensional(3D) layer-pillar framework with rectangular channels, while complex 2 displays a two-dimensional(2D) wave net architecture. Furthermore, 1 and 2 were characterized by elemental analysis, infrared spectra(IR), thermal gravimetric analyses(TGA) and fluorescence measurements. The luminescent properties of 1 dispersed in various organic solvents have been investigated systematically, demonstrating high selectivity for acetone via the fluorescence quenching effect.     

Two Coordination Polymers Based on Pamoic Acid and(1,4-Bis(imidazol-1-yl)-butane: Synthesis,Structures and Properties

Two mixed-ligand compounds,namely[Mn_2(bimb)(PA)_2]_n (1) and[Zn(bimb)(PA)]_n (2)(H_2PA=pamoic acid,bimb=1,4-bis(imidazol-1-yl)-butane) have been synthesized under the same solvothermal conditions.Compound 1 can be described as (4,4) topology based on the 4-connected[Mn_2(COO)_4]paddle-wheel units,which contains both rotaxane-and catenane-like motifs.For 2,the 2D wavy-like network interlocked with each other and resulted in a 2-fold interpenetrated 2D→3D architecture.The structural differences of the two compounds are mainly due to the differences of metal ions and coordination modes of the PA~(2-)ligand.In addition,the magnetism and photoluminescent properties of them have also been explored.     

Temperature-dependent Hydrothermal Synthesis of Two Distinct Three-dimensional Copper Complexes

Two distinct copper coordination polymers, namely [Cu~Ⅱ_2(2,5-pydc)_2(bpp)_2]·H_2O(1) and Cu_2~ⅠCu~Ⅱ(2,5-pydc)_2(bpp)_2(2)(2,5-pydc = pyridine-2,5-dicarboxylic acid, bpp = 1,3-bi(4-pyridyl)propane), have been successfully synthesized through hydrothermal conditions under different temperatures. Single-crystal X-ray structural analysis revealed that both complexes 1 and 2 are 3D frameworks. Complex 1 is an 8-connected 2-fold interpenetrating network based on [Cu(2,5-pydc)]_4 molecular building block(MBB), and also can be simplified as a 4-connected net if the Cu(Ⅱ) ion is regarded as an independent node, whereas 2 shows a(4,4)-connected non-interpenetrated framework which contains mixed valence Cu(Ⅰ/Ⅱ) centers. The results demonstrate that temperature plays a significant role in the final structures of the complexes.