Three Novel Luminescent Zinc(Ⅱ) Compounds Constructed by Employing Mixed-ligand Strategy

Three novel coordination polymers,[Zn(suc)(o-bix)]_n (1),[Zn(suc)(m-bix)·H_2O]_n (2) and[Zn_2(suc)_2(p-bix)_2·4H_2O]_n (3)(H_2suc=succinic acid,o-bix=1,2-bis(imidazol-1-ylmethyl)-benzene,m-bix=1,3-bis(imidazol-1-ylmethyl)-benzene,p-bix=1,4-bis(imidazol-1-ylmethyl)-benzene),have been synthesized and structurally characterized by elemental analysis,IR spectroscopy,thermogravimetric analysis,powder X-ray diffraction,and single-crystal X-ray diffraction.These three coordination polymers present various structures originated from auxiliary N-donor ligands with different configurations.Compound 1 shows a 2D network with4~4-sql topology.Compound 2 exhibits an infinite chain,and the adjacent chains are extended into a 2D sheet byπ-πstacking interactions.Changing the conformation of the N-donor ligand leads to 3 featuring a 3D framework with a novel 4-connected (6~5·8) topology.In addition,the solid-state photoluminescent properties of compounds 1～3 are investigated.     

Synthesis and Crystal Structure of a New Zinc(Ⅱ) Coordination Polymer Assembled by 4-Nitrophthalic Acid and Bis(imidazol) Ligands

A new complex [Zn(4-nph)(bib)]_(2n)·nH_2O(1) has been obtained by the reaction of metal(Zn(Ⅱ)),1,4-bis(imidazol-1-yl)-butane(bib) with 4-nitrophthalic acid(4-H_(2nph)).The crystal structure of 1 has been determined by single-crystal X-ray diffraction analysis.Compound 1 is of triclinic system,space group P1 with a = 10.3251,b = 12.4503,c = 16.6497 ?,α = 88.487(3),β = 72.529(3),γ = 79.991(3)°,V = 2009.8(5) ?~3 and Mr = 945.47.Complex 1 shows a three-dimensional(3 D) framework.Moreover,through intermolecular hydrogen bonds,compound 1 is assembled into a supramolecular structure.The thermal stability and luminescent properties of 1 are also investigated.     

Two Zn(Ⅱ)/Cd(Ⅱ) Metal-organic Frameworks Constructed from 1,3,5-Benzenetricarboxylic Acid and1,4-Bis(1-imidazolyl)benzene:Syntheses,Structures and Photoluminescent Properties

Two new d~(10 )metal-based metal-organic frameworks,{[Zn_3(btc)_2(bib)_2(H_2O)_2]·2H_2O}_n(1)and{[Cd_3(btc)_2(bib)_(1.5)(H_2O)_6]·6H_2O}_n(2)(btc=1,3,5-benzenetricarboxylate anion,bib=1,4-bis(1-imidazolyl)benzene)have been prepared under hydrothermal conditions by the reactions of d~(10 )metal oxides of ZnO and CdO with the aromatic polycarboxylic H_3btc and the N-heterocyclic bib.The two products were characterized by single-crystal X-ray diffraction analysis,elemental analysis,thermogravimetric analysis(TGA),and IR spectroscopy.Complexes 1 and 2 crystallize in monoclinic C2/c and triclinic P 1 space groups,respectively.1 shows a 3D framework,and the potential large voids of the 3D network lead to a 3-fold interpenetrating architecture.2 displays a 2D framework,and the adjacent 2D layers expand into a 3D supramulecular network via rich hydrogen bonds.Moreover,the luminescent properties of the two complexes are investigated in solid state.     

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.     

Synthesis,Structure and Luminescent Property of a New bnn-type Zn(Ⅱ) Coordination Polymer

A new Zn(Ⅱ) coordination polymer, namely [Zn(Htci)(bib)0.5(H2O)]n·nH2O(1, H3 tci = tri(2-carboxyethyl)isocyanurate, bib = 1,4-bis(imidazol-1-ylmethyl)-butane) has been synthesized by combining H3 tci and bib ligands with Zn(Ⅱ) salts under solvothermal conditions. The title compound crystallizes in monoclinic, space group P21/c with a = 13.3424(7), b = 7.9051(5), c = 20.4650(12) , β = 101.935(5)o, V = 2111.8(2) 3, C17H24N5O11 Zn, Mr = 539.8, Z = 4, Dc = 1.698 g/cm3, F(000) = 1116, μ = 1.236 mm-1, the final R = 0.0398 and wR = 0.00879 for 3722 observed reflections(I 2■(I)). X-ray structural analysis reveals that compound 1 exhibits a three-dimensional(3D) pillar-layered framework, and can be simplified into a 5-connected bnn topological network. Moreover, the luminescent properties for compound 1 were also studied at room temperature.     

Syntheses,Structures and Catalytic Properties of Two Mn(Ⅱ) and Cd(Ⅱ) Coordination Polymers through in Situ Ligand Reaction

Two coordination polymers, namely [Mn(μ-Hcpia)(bipy)(H_2O)_2]_n(1) and [Cd_3(μ_3-Hcpia)_2(μ-Hbiim)_2(μ-H_2biim)(H_2O)_2]_n(2), have been constructed hydrothermally using H_2cbia(H_2cbia = 5-(4'-cyanobenzoxy)isophthalic acid), bipy(bipy = 4,4'-bipyridine), H_2biim(H_2biim = 2,2'-biimidazole), and manganese or cadmium chlorides at 160℃. Interestingly, the H_3cpia(H_3cpia = 5-(4'-carboxylphenoxy)isophthalic acid) ligand was generated by in situ hydrolysis of cyano group in H_2cbia. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses(TGA), and single-crystal X-ray diffraction analyses. Both compounds crystallize in the triclinic system, space group P1. Compound 1 discloses a 1D linear chain of the 2C1 topological type. Adjacent chains are assembled into a 2D supramolecular sheet through O–H···O/N hydrogen bonds. Compound 2 features a 3D framework with a 3,4,4 T25 topology. The luminescent and catalytic properties of two compounds were investigated. Compound 1 exhibits a superior catalytic activity in the cyanosilylation at room temperature.     

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.     

Solvothermal Syntheses,Crystal Structures,and Luminescent Properties of Three Coordination Polymers Derived from Semirigid 3-(Carboxymethyl)benzonic Acid and Dipyridyl Coligands

Three coordination polymers, namely, {[Zn(cmba)(bpp)]×H_2O}_n(1), {[Zn(cmba)(bpa)1.5]×2.25H_2O}_n(2) and {[Cd(cmba)(bpa)(H_2O)]×H_2O}_n(3)(H_2cmba = 3-(carboxymethyl)benzonic acid, bpp = 1,3-bis(4-pyridyl)propane and bpa = 1,2-bi(4-pyridyl)ethane), were synthesized under solvothermal conditions and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis(TGA), and single-crystal X-ray diffraction. Complex 1 features a 2D(4,4) grid layer with a side length of 9.827(10)/12.176(13) ?. Complex 2 shows a 2D → 2D 2-fold interpenetrating layer structure through the flexible bpa coligands. Compound 3 presents a 2D layer formed from the metal-carboxylate chains further extending through bpa pairs. Furthermore, the solid state luminescent properties of complexes 1~3 were investigated at room temperature.     

Hydrothermal Synthesis,Crystal Structure and Luminescent Property of a Cd(Ⅱ) Compound with(4,6)-Connected Topology

A new Cd(Ⅱ) coordination polymer, namely {Cd_2(L)(biimpy)(H_2O)}_n(1, H4 L = 3-(3?,5?-dicarboxylphenoxy)phthalic acid, biimpy = 2,6-bis(1-imdazoly)pyridine), has been successfully synthesized via the hydrothermal reactions of Cd(Ⅱ) ions, H_4L and biimpy. The crystal structure is of triclinic, space group P1 with a = 7.7874(5), b = 9.9716(5), c = 18.5278(6) ?, α = 91.327(4), β = 96.689(4), γ = 111.896(5)o, V = 1322.39(12) ?~3, C_(27)H_(17)Cd_2N_5O_(10), M_r = 796.26, Z = 2,D_c = 2.000 g/cm~3, F(000) = 780, μ = 1.679 mm~(-1), R = 0.0345 and wR = 0.0767 for 3890 observed reflections(I 2s(I)). Single-crystal X-ray structural analysis reveals that compound 1 features a three-dimensional(3D) framework based on two different dinuclear [Cd_2(COO)_2] building subunits, and topological analysis shows that it can be simplified into a binodal(4,6)-connected topological network with the point symbol of {3.4~2.5~2.6}{3~2.4~2.5~2.6~4.7~4.8}. Moreover, the thermal stability and luminescent property of compound 1 were also studied.     

Structure and Photochemical Properties of a Chiral Cd Coordination Polymer Based on 4,4'-(Hexafluoroisopropylidene) Bis(benzoic acid) and 1,3-Di(pyridineyl)benzene

One new chiral metal-organic coordination polymer,[Cd_2(dpb)(H_2hfipbb)_2]_n,was obtained under hydrothermal conditions of 1,3-di(pyridineyl)benzene(dpb) and 4,4'-(hexafluoroisopropylidene)bis(benzoic acid)(H_2hfipbb). The title compound reveals a three-dimensional(3D) framework with two types of helical chains [Cd(COO)]n,which are linked each other to further form a double helical chain [Cd_2(COO)_2]_n by sharing the same Cd(Ⅱ) ions. The dpb connects the double helical chains to generate a 3D framework. These unique structures were studied by single-crystal X-ray and other spectroscopy techniques. In addition,the luminescent,fluorescence lifetime and second harmonic generation efficiency properties in the solid state have been studied.     

Crystal Structure and Luminescent Properties of a 3D Cd(Ⅱ) Compound Constructed from Succinate and 3,6-Di(4-pyridyl)pyridazine

A three-dimensional(3D) coordination polymer,[Cd(SC)(DPPD)]_n(1,H_2SC = succinic acid and DPPD = 3,6-di(4-pyridyl)pyridazine),has been synthesized by the solvothermal reaction of Cd(NO_3)_2·4H_2O with H_2 SC and DPPD at 120 oC in DMF solvent. Compound 1 crystallizes in the monoclinic system,space group P2_1/c,with a = 10.7993(4),b = 11.7705(3),c = 13.5336(6) ?,V = 1678.89(11) ?~3,Z = 4,C18H14N4O_4 Cd,M_r = 462.73,D_c = 1.831 g/cm~3,μ = 1.335 mm~(-1),F(000) = 920.0,the final R = 0.0500 and wR = 0.1567 for 3714 observed reflections with I 2s(I). In compound 1,the Cd(Ⅱ) ions are linked by the SC~(2–) ligands to give a two-dimensional(2D) undulating sheet based on the centrosymmetric dinuclear Cd_2(COO)_2 units. The 2D sheets are further connected by the DPPD ligands to produce a 3D structure,which is a 6-connected(4~4·6·~(10)·8) topological network based on the dinuclear Cd_2(COO)_2 node. Compound 1 exhibits a photoluminescent emission with a maximum at 540 nm upon excitation at 460 nm.     

Three New Isostructural Metal-organic Coordination Polymers from Triangular Pyridinedicarboxylate Ligand:Syntheses,Structures and Properties

Three new isostructural coordination polymers, namely, [Mg(cpna)(H_2O)_2]_n(1), [Mn(cpna)(H_2O)_2]_n(2) and [Co(cpna)(H_2O)_2]_n(3)(H_2 cpna = 5-(3-carboxylphenyl)nicotic acid) are reported. They were synthesized by hydrothermal reactions of transition metal or alkaline earth metal chloride with 5-(3-carboxylphenyl)nicotic acid,respectively. Complexes 1～3 exhibit 2D layers with a 3,3-connected topology with Schl?fli symbol {4.82}. Such layers including hexagonal rings and a quadrangular ring are further extended into an ordered 3D framework by hydrogen bonds between the cpna~(2-) ligands and water molecules. The rare complex 1 has excellent luminescence and can be used as luminescent materials, while 2 and 3 possess prominent magnetism with potential applications in magnetic materials.     

A Zn(Ⅱ) Coordination Polymer with 4-Connected bbf Topology: Synthesis,Crystal Structure and Luminescent Property

A new Zn(Ⅱ) compound, namely {Zn(BTA)(pdc)_(0.5)}_n(1, HBTA = 1,2,3-benzotriazole, H_2pdc = terephthalic acid), has been hydrothermally synthesized and characterized by elemental analysis, infrared analysis, powder X-ray diffraction analysis and single-crystal X-ray structural analysis. The crystal structure is of monoclinic system, space group P21/c with a = 10.751(3), b = 9.792(3), c = 9.292(3) ?, β = 95.391(4)°, V = 973.9(5) ?3, C10H6N3O2 Zn, Mr = 265.57, Z = 4, Dc = 1.811 g/cm3, F(000) = 532, μ = 2.506 mm-1, R = 0.0221 and w R = 0.0605 for 2075 observed reflections(I 2s(I)). Single-crystal X-ray structural analysis reveals that compound 1 features a three-dimensional(3D) framework with 4-connected bbf topology. Moreover, the thermogravimetric(TG) analysis and photoluminescent property of 1 were also discussed.     

Two N-donor Auxiliary Ligands Mediated Zn(Ⅱ) Coordination Polymers Incorporating 5-Nitro-1,2,3-benzenetricarboxylate Ligand: Syntheses,Crystal Structures,and Luminescent Properties

Two N-donor auxiliary ligands mediated Zn(Ⅱ) coordination polymers, namely, {[Zn(Hnbta)-(bimm)](3H_2O)}_n(1) and {[Zn_(1.5)(nbta)(pyim)(H_2O)](2H_2O)}_n(2)(H_3nbta = 5-nitro-1,2,3-benzenetricarboxylic acid, bimm = bis(imidazol-1-yl)methane and pyim = N-(4-pyridylmethyl)imidazole), have been prepared by the hydrothermal reaction. Their structures were determined by single-crystal X-ray diffraction analysis, elemental analyses and infrared spectra. Compound 1 possesses a one-dimensional(1D) chain structure, while compound 2 features a two-dimensional(2D) network. In addition, they both exhibit high thermal stabilities and photoluminescent properties in the solid, and can be explored as potential luminescent materials.     

A New 3-Fold Interpenetrating 3D Zn(Ⅱ) Metal-organic Framework: Synthesis,Structure and Luminescent Property

A new Zn(Ⅱ) coordination polymer,namely {[Zn_(1.5)(1,3,5-btc~(3-))(dtb)(H_2O)](H_2O)_2}_n(1)(1,3,5-H_3btc = 1,3,5-benzenetricarboxylic acid,dtb = 1,3-di-(1,2,4-triazole-4-yl)benzene),has been hydrothermally synthesized and structurally characterized. X-ray single-crystal diffraction determination reveals that 1 crystallizes in the monoclinic C2/c space group with a = 33.811(12),b = 8.406(2),c = 17.296(4) ?,β = 120.593(2)°,V = 4232(2) ?~3,Z = 4,Mr = 1142.88,Dc = 1.794 Mg/m~3,μ = 1.783 mm~(-1),F(000) = 2320,the final R = 0.0338 and wR = 0.0827 for 3043 observed reflections with I 2σ(I). Compound 1 exhibits 1D Zn(Ⅱ)-carboxylate chains,which are connected into a 3D porous framework with large channels by dtb,and then three identical 3D networks are interpenetrated with each other. In addition,the luminescence property of the complex has also been investigated.     

Structure and Photophysical Properties of a Chiral 4-Fold Interpenetrated Zn(Ⅱ) Coordination Polymer Tuned by 4,4'-(Hexafluoroisopropylidene)bis(benzoic acid) and 1,3-Di(pyridineyl)benzene

A new three-dimensional(3D) chiral metal-organic coordination polymer, [Zn(dpb)(hfipbb)]n, was obtained under hydrothermal conditions by 1,3-di(pyridineyl)benzene(dpb) and 4,4?-(Hexafluoroisopropylidene)bis(benzoic acid)(H_2hfipbb). The as-prepared sample was characterized by single-crystal X-ray diffraction, PXRD, elemental analysis, IR spectroscopy and TGA analysis. The title coordination polymer crystallizes in orthorhombic, space group P21212, with a=21.923(4), b=23.594(4), c=7.3042(13) ?, V=3778.1(12) ?~3, Dc=1.209 g/cm~3, Mr=687.90, F(000)=1328, μ=0.713 mm~(-1) and Z=4. The compound contains two types of helical chains [Zn(hfipbb)]n and [Zn(dpb)]n which are linked with each other to generate a 3D framework by sharing the same Zn(Ⅱ) cations. It displays a 4-fold interpenetrated 3D framework. In addition, the luminescence, fluorescence lifetime and the second harmonic generation(SHG) efficiency properties in the solid state have been studied.     

Impact of the flexibility of pillar linkers on the structure and CO_2 adsorption property of ‘‘pillar-layered' MOFs

A new metal–organic framework {[Zn_2(bpta)(bpy-ee)(H_2O)_2]·x solve}_n(1)(H_4bpta = biphenyl-2,20,6,60-tetracarboxylic acid and bpy-ee = 1,2-bis(4-pyridyl)ethylene) has been obtained under hydrothermal condition, and structurally characterized by single-crystal X-ray diffraction. Complex 1 reveals a threedimensional(3D) ‘‘pillar-layered' framework with non-flexible linker, in which some different structure characters can be found compared to that of some related other ‘‘pillar-layered' MOFs based on flexible pillar linkers. It demonstrates the impact of the flexibility of pillar linker on the final structure in this system. In addition, the selective CO_2 adsorption performance of 1 was also investigated.     

Two New Coordination Polymers Based on H_4BIPA-TC: Syntheses and Fluorescence Sensing for Nitroaromatic Compounds and Fe~(3+) Ion

Based on the solvothermal reaction of 5,5'-(1,3,6,8-tetraoxobenzo[lmn][3,8] phenanthrolin-2-7-diyl)bis-1,3-benzenedicarboxylic acid(H_4L) linker and Zn(Ⅱ)/Cd(Ⅱ), two new 2 D coordination polymers(CPs), namely {[ZnH_2L(4,4'-bibp)]·H_2O}_n(1) and {[CdL_(0.5)(1,4-bimb)_(0.5)(H_2O)]·EtOH}n(2)(L = BIPA-TC), have been successfully constructed and characterized by EA, PXRD and IR with the aid of 4,4'-bis(benzoimidazo-1-yl)biphenyl(4,4'-bbib)/1,4-bis(imidazol-1-ylmethyl)benzene(1,4-bimb). The structural analysis showed that complex 1 exhibits a 3D supramolecular structure with the topology of sql, and complex 2 possesses a 2-nodal(4,6)-c framework with the topology of(3~2·4~2·5~2)(3~4·4~4·5~4·6~3)-4,6 T26. Fluorescent experiments showed that 1 and 2 have high selectivity and sensitivity for the sensing of nitroaromatic compounds and Fe~(3+) in aqueous solutions.     

Syntheses,Structures, and Properties of Three Coordination Polymers: [Cd_2(bpp)_(1.5)(Hbpp)(phen)_2]_n, [Mn_3(Htptc)_2(phen)_2(H_2O)_2]_n,and {[Cu(btc)_(0.5)(1,4-bib)]·2H_2O}_n

Hydrothermal reactions of three aromatic polycarboxylic acids and the transitional metal cations in the presence of phen and 1,4-bib afford three new coordination polymers: [Cd2(bpp)1.5(Hbpp)(phen)2]n(1), [Mn3(Htptc)2(phen)2(H2O)2]n(2), and {[Cu(btc)0.5(1,4- bib)]·2H2O}n(3)(H2bpp = 2,6-bis(4'-carboxyphenyl)-4-phenylpyridine, H4tptc = terphenyl-2,5,2',5'-tetracarboxylic acid, H4btc = biphenyl-2,2',4,4'-tetracarboxylic acid, phen = 1,10-phenanthroline, and 1,4-bib = 1,4-bis(1H-imidazol-1-yl)benzene). Their structures have been determined by singlecrystal X-ray diffraction analyses, elemental analyses, IR spectra, and powder X-ray diffraction(PXRD) analyses. In compound 1, the CdII cations are linked by bpp2- to form one ladder structure, based on which a 3D network is constructed with the help of non-covalent interactions. The topology of 2 is a 3D(3,4,5)-connected framework with the Point Schl?fli symbol of(42.6)32(4.62.8)(45.64.8)2. Compound 3 shows an unprecedented 3D(4,4)-connected framework with the Point Schl?fli symbol of(64.82)2(65.8). Moreover, the luminescent property of 1 has been investigated.     

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.