Syntheses,Structures, and Luminescent Properties of Two Zn~Ⅱ-organic Polymers Based on [Zn(ox)]_n Chains and Different Imidazole Linkers

Hydrothermal reactions of two imidazole derivatives(1,3,5-tib = 1,3,5-tris(1Himidazol-1-yl)benzene, 1,4-bimb = 1,4-bis(1H-imidazol-1-ylmethyl)benzene) and the ZnⅡ cations in the presence of oxalic acid(H2ox) afford two coordination polymers, namely, {[Zn(ox)(1,3,5-tib)]·2(H2O)}n(1) and [Zn1.5(ox)1.5(1,4-bimb)1.5]n(2). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, and powder X-ray diffraction(PXRD) analyses. Both complexes 1 and 2 are based on the 1D zigzag [Zn(ox)]n chains, and their final structures are controlled by the two different imidazole linkers, which expanded the structure along different directions, finally giving a 3D dia net for 1 and a 2D sql layer for 2. Moreover, the luminescent properties of 1 and 2 have been investigated.     

A Novel 3D Twofold Zn(Ⅱ) Coordination Polymer Constructed by Mixed Flexible Ligands: Synthesis,Crystal Structure and Fluorescence Property

A new Zn(Ⅱ) coordination polymer, {[Zn(1,3-bip)(oba)]·0.5H_2O}n(1),1,3-bip =1,3-bis(imidazole)propane, H_2oba=4,4?-oxybis(benzoate)), have been synthesized and characterized by single-crystal X-ray diffraction, powder XRD, FTIR, TGA and elemental analysis techniques. The single-crystal X-ray diffraction reveals that complex 1 shows a 3D→3D twofold interpenetrating network that can be described as a 4-connected uninodal net with(65.8) topology. In addition, the photoluminescence property of complex 1 was also investigated at room temperature.     

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.     

One New 3D Pillared-layer Ag(Ⅰ)-Coordination Framework Based on a Unique 1D Ag_2O_2 Ribbon: Synthesis,Crystal Structure and Luminescent Properties

A new 3D Ag(I) coordination polymer {[Ag(AZDB)_(0.5)(bpe)_(0.5)]·H_2O}_n(1) has been papared by azobenzene-3,3?-dicarboxylicate(H_2AZDB), 1,2-bis(4-pyridyl)ethylene(bpe) and silver salts via hydrothermal method. The compound was fully characterized by single-crystal X-ray diffraction, elemental analyses, infrared spectrum(IR), powder X-ray diffraction(PXRD) and thermogravimetric analysis(TGA). The strucrural analysis indicate that compound 1 shows a 3D pillared-layer framework constructed from a unique 1D Ag_2O_2 ribbon and pyridyl/carboxylicate mixed system, which features a 2-nodal(4, 6)-connected fsc net with a(44·610·8)(44·62) topology.Moreover, the photoluminescent properties have also been discussed.     

Synthesis, structure and photoluminescent property of a novel potassic compound

A novel 3D coordination compound of K(H2TDA)(H20)(1)(H_3TDA=1H-1,2,3-triazole-4,5-dicarboxylic acid) has been prepared and characterized by IR spectroscopy,elemental analysis,ICP and single-crystal X-ray diffraction.Compound 1 displays strong fluorescent emission at room temperature.     

A New Co(Ⅱ) Coordination Compound Constructed by Tripyridyltriazole and Pyromellitic Acid:Synthesis,Crystal Structure and Antifungal Activity

A new coordination compound, [Co(L~(223))_2(H_2O)_2]·H_2pm(1, L~(223) = 3,4-bis(2-pyridyl)-5-(3-pyridyl)-1,2,4-triazole and H4 pm = pyromellitic acid), has been synthesized. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, IR spectrum analysis and thermogravimetric analysis. Single-crystal X-ray diffraction analysis reveals that complex 1 belongs to the triclinic system, space group P1 with a = 10.2470(8), b = 10.2879(9), c = 10.2951(11) ?, α = 109.398(2), β = 97.6590(10), γ = 95.3260(10)°, V = 1003.60(16) ?3, Z = 1, Dc = 1.565 g/cm~3, μ = 0.508 mm~(-1), Mr = 945.73, F(000) = 485, the final R = 0.0562 and w R = 0.0783 with I 2σ(I). Two L223 as chelating ligands link one Co(II) ion to form a 0D motif. Furthermore, the 0D motifs are linked into a 2D coordination pattern with hydrogen bonds. In addition, the antifungal effects of the ligand and the complex were evaluated by the disc diffusion method against Colletotrichum gloeosporioides Penz. 1 represents antifungal activity with high levels of inhibitory potency which is larger than the corresponding ligand.     

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.     

Synthesis and Crystal Structure of a Novel Ca(Ⅱ) Coordination Polymer Containing Dipyridine Dicarboxylic Ligand

The novel alkaline metal complex Ca(BPDCH)2(1, BPDCH2 = 2,2'-bipyridine-5,5'-dicarboxylic acid) has been synthesized by the hydrothermal reaction of Ca(NO3)2·4H2O with 2,2'-bipyridine-5,5'-dicarboxylic acid. The molecular and crystal structures of complex 1 have firstly been characterized by FTIR, elemental analysis, and X-ray single-crystal diffraction. The 3D MOF structure of complex 1 was interpreted by the versatile binding modes-the intermolecular hydrogen bonds and π-π stacking interactions of 2,2'-bipyridine-5,5'-dicarboxylic acid ligand. The analysis results show complex 1 belongs to a coordination polymer with 3D MOF structure. The results of thermogravimetric analysis and solubility demonstrate complex 1 is a thermostable compound and does not dissolve in water and traditional organic solvents.     

Synthesis,Crystal Structure and Luminescent Property of a Ag(Ⅰ) Coordination Polymer with a 3D Sandwich-like Framework

A new coordination polymer,{[Ag_2(bpp)_2(H_2O)_2]·bpdc·3H_2O}_n,derived from the ligand biphenyl-4,4'-dicarboxylic acid(H_2bpdc),has been obtained through a hydrothermal technique(bpp = l,3-bis(4-pyridyl)propane).Its single-crystal structure has been characterized by single-crystal X-ray diffraction,powder XRD,FT-IR,TGA and elemental analysis techniques.The single-crystal X-ray diffraction reveals that complex 1 consists of 1D infinite[Ag(bpp)(H_2O)]_n~(n+)cationic chains,2D anionic layer constructed by bpdc anions and free water which provide charge compensation in the crystal structure.The 1D infinite[Ag(bpp)(H_2O)]_n~(n+) cationic chains and 2D anionic layer are further stacked in-ABAB- fashion through intermolecular H-bonding to form a 3D sandwich-like framework.In addition,the luminescent property of complex 1 in the solid state at room temperature was investigated.     

A Zn(Ⅱ) Coordination Polymer Based on a Flexible Symmetric Multicarboxylate Ligand

A novel coordination polymer, namely [Zn_2(CAPA)(DMA)(H_2O)]_(2n)·n(H_2O)(1,H_4CAPA = 5-(bis(4-carboxybenzyl) amino) isophthalic acid, DMA = N,N-dimethylacetamide) has been synthesized through a solvothermal method and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectra, and thermogravimetric analyses. The crystal structure is of monoclinic, space group P21/n with a = 8.0585(5), b = 18.9733(10), c = 20.2044(14) ?, β = 101.144(7)o, V = 3030.9(3) ?~3, C_(56)H_(54)Zn_4N_4O_(21), M_r = 1378.58, Z = 2). The compound forms a three-dimensional(3D) supramolecular framework by linking adjacent layers via hydrogen bonds and π···π interactions. It is interesting that the crystal structure is much related to the flexibility and configuration of the ligand. In addition, the thermal stability and luminescence properties for the compound have also been investigated.     

Two Cd(Ⅱ) Coordination Polymers Based on a Flexible Tricarboxylate Ligand: Syntheses,Structures, and Photoluminescence and Catalytic Properties

Studies on the synthesis and design of coordination polymers(CPs) with flexible ligands are of great interest owing to their dynamic structures and promising applications. The title coordination polymers, {[Cd·(HTTTA)·(phen)]·2H_2 O}n(1) and [Cd·(HTTTA)·(phen)]n(2)(H3 TTTA = 2,2',2'-[1,3,5-triazine-2,4,6-triyltris(thio)] tris-acetic acid, phen = 1,10-phenanthroline) have been synthesized and characterized by elemental analysis, IR, powder XRD and single-crystal X-ray diffraction. Complex 1 consists of one CdII ion, one HTTTA2-ligand and one phen co-ligand. The Cd(Ⅱ) metal clusters were bridged by the tridentate HTTTA2-ligands into infinite 1D chains, which are further connected into the 3D architecture by abundant hydrogen bonds. In 2, three carboxyl groups of HTTTA2-ligand show different coordination directions because of the C–S–C flexible bond angle, which leads to different 1D chains of 2. The strong π-π stacking interaction and four C–H···O hydrogen bonds connect the 1D chains into a 3D framework. The solid-state photoluminescence and catalytic properties were studied as well.     

Synthesis,Crystal Structure,Fluorescent Property and DFT Calculations of a New Zn(Ⅱ) Complex Based on 3-(2-Pyridyl)-5-(4-pyridyl)-1H-1,2,4-triazole

A new coordination compound Zn(2,4?-bpt)2(H_2O)(1) based on the versatile ligand 2,4?-Hbpt(2,4?-Hbpt = 3-(2-pyridyl)-5-(4-pyridyl)-1H-1,2,4-triazole) was prepared by hydrothermal reactions. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, X-ray powder diffraction, IR spectrum analysis and thermogravimetric analysis. Single-crystal X-ray diffraction analysis indicates that the complex belongs to monoclinic system, space group C2/c with a = 23.877(3), b = 0.7483(9), c = 1.2492(2) ?, b = 92.681(2)°, V = 2230.6(4) ?3, Z = 4, Dc = 1.572 g/cm~3, m = 1.143 mm~(-1), Mr = 527.85 and F(000) = 1080. The final R = 0.0581 and w R = 0.0898 with I 2s(I). 1 is a 0D motif which is connected by hydrogen bonds to form a corrugated 1D pattern. In addition, 1 shows strong photoluminescent emissions in the solid state at room temperature which can be used as potential optical materials. Theoretical calculations based on density functional theory(DFT) were employed in order to explicate the stability and chemical reactivity of 2,4?-Hbpt with different conformations. The results indicated that conformation I is more stable and prior to coordination in the reactions.     

Synthesis,Structure and Luminescent Property of a New Zn(Ⅱ) Coordination Polymer Based on 1,3,5-Benzenetricarboxylate and 4,4'-Bipyridine Ligands

A new Zn(II) coordination polymer [Zn3(BTC)2(4,4'-bpy)(CO)2]n(1, H3 BTC =1,3,5-benzenetricarboxylic acid, 4,4'-bpy = 4,4'-bipyridine) has been prepared through urothermal reaction of zinc nitrate hexahydrate with 1,3,5-benzenetricarboxylic acid and 4,4'-bipyridine, and characterized by elemental analysis, IR spectroscopy, TGA and powder XRD, and its crystal structure was determined by single-crystal X-ray diffraction analysis. The title compound crystallizes in the monoclinic system, space group C2/c, with a = 10.262(3), b = 18.838(5), c =15.083(4) A, β = 99.203(4)o, V = 2878.3(14) A3, C30H14Zn3N2O14, Mr = 822.54, Z = 4, Dc = 1.898g/cm3, μ = 2.561 mm-1, F(000) = 1640, R = 0.0363 and w R = 0.0932 for 2828 observed reflections(I 2σ(I)). X-ray analysis shows that the asymmetric unit of the title compound contains two crystallographically unique Zn(II) atoms which are connected by BTC3- ligands and 4,4'-bpy coligands to form a 3D framework with 1D channels. The solid luminescence of ligand and the title complex was also studied at room temperature.     

Syntheses,Structures and Properties of Two Mn(Ⅱ) Clusters Based on 1,10-Phenanthroline-2,9-dicarbaldehyde Dioxime Ligand

Two novel clusters [Mn~Ⅲ_3(μ_3-O)(phendox)3]X·13H_2O(X = Cl(1), Br(2]) have been obtained from the solvothermal reactions of 1,10-phenanthroline-2,9-dicarbaldehyde dioxime(H_2phendox) with MnCl_2·4H_2O or anhydrous MnBr_2, and their structures were characterized by elemental analysis, FT-IR, XRD, TGA, MS and single-crystal X-ray diffraction. It crystallizes in trigonal, space group P3_1/c. X-ray analysis reveals that the neighbouring [Mn_3(μ_3-O)(phendox)_3]+ cores are linked by C–H···Cl hydrogen bonds and form an infinite supramolecular chain along the c-axis. Neighbouring chains are packed with each other by off-set p-p interactions of the aromatic rings on phenox2-. A 3D supramolecular architecture in a honeycomb topology is formed with 1D hexagonal channel in the dimensions of 13? × 13? along the c-axis. The gas adsorption studies show that compound 1·13H_2O is stable upon the removal of guest molecules and the desolvated compound absorbed considerable amount of CO_2.     

One Pillared Layered Zn(Ⅱ) Coordination Compound Based on 2,6-Naphthalenedicarboxylic Acid: Synthesis,Structure and Luminescent Property

One new pillared layered zinc hydroxide {Zn_4(OH)_6(ndc)·2(H_2 O)}_n,(H_2 ndc =2,6-na-phthalenedicarboxylic acid) has been achieved under hydrothermal conditions by using2,6-na-phthalenedicarboxylic acid, 2,4-diami-6-phenyl-1,3,5-triazine as well as Zn(OAc)_2·2 H_2 O,and structurally characterized by X-ray single-crystal diffraction, IR spectra, elemental analysis,powder X-ray diffraction(PXRD) and thermogravimetric analysis(TGA). The X-ray single-crystal diffraction proves that the title compound is in monoclinic system, space group P2_1/c with a =16.362(8), b = 9.324(5), c = 5.364(3) ?, β = 99.081(9)°, V = 808.1(7) ?~3, D_c = 2.522 g/cm~3, M_r =613.73, Z = 2, F(000) = 608, μ = 5.935 mm~(-1), GOOF = 1.050, R = 0.0469 and wR(Ⅰ 2σ(Ⅰ)) =0.1291. In the title compound, the tetrahedral and octahedral zinc atoms are connected by μ_3-OH groups to form zinc hydroxide inorganic layers extending parallel to the bc-plane. The adjacent layers are pillared by the connection of Zn2 atoms with ndc~(2-)ligands to construct a three-dimensional(3D) structure; meanwhile, the interactions of five hydrogen bonds make the 3D network structure more stable. Furthermore, the title compound exhibits luminescent property at solid state.     

A New 2D Layered Barium Coordination Polymer [Ba（3-NPA）]n： Synthesis,Crystal Structure,Thermal Stability and Luminescent Properties

A new two-dimensional(2D) barium(Ⅱ) coordination polymer [Ba(3-NPA)]n(1) has been obtained by the hydro/solvothermal reaction of the corresponding metal salt with 3-nitrophthalic acid(3-NPAH2). Compound 1 was characterized by infrared spectrum, elemental analysis, powder X-ray diffraction(PXRD) and single-crystal X-ray diffraction analysis. Compound 1 crystallizes in triclinic, space group P1 with a = 4.9611(3), b = 7.2599(4), c = 12.9463(8) , α = 89.0892(2), β = 80.546(2), γ = 73.211(2)°, V = 440.1(5) 3, Z = 2, C8H3BaNO6, Mr = 346.45, Dc = 2.614 g·cm-3, μ = 4.526 mm-1, S = 1.035, F(000) = 324, R = 0.0168 and wR = 0.0471 for 1712 observed reflections with I 2λ(I).(Δρ)max = 0.458,(Δρ)min =-0.565 e·-3 and(Δ/σ)max = 0.001. In compound 1, each 3-NPA2- ligand links six Ba(ΙΙ) ions and each Ba(ΙΙ) ion attaches to six 3-NPA2- ligands to form an inorganic layer structure in the ab-plane. The phenyl groups of 3-NPA2- ligands are grafted on the two sides of the inorganic layer, resulting in a two-dimensional(2D) layered structure. Furthermore, the thermal stability and luminescent properties of compound 1 have also been investigated in detail.     

Mixed-solvothermal Synthesis,Crystal Structure and Luminescence of a New Dinuclear Yttrium(Ⅲ) Coordination Polymer with 1-D Wave-like Infinite Chains

A new dinuclear Y~(3+) coordination polymer{[Y_2(H_2O)_2(C_(14)H_8O_4)_3(C_(12)H_8N_2)_2]·3 H_2O}_n (1, C_(14)H_8 O_4 = 2,2?-biphenyldicarboxylate, phen = 1,10-phenanthroline), has been obtained by means of a mixed-solvothermal method using ethylene glycol and water as solvent. The compound was characterized by elemental analysis, energy-dispersive X-ray spectroscopy(EDS), IR spectrum and single-crystal X-ray diffraction. The results reveal that 1 belongs to monoclinic system, space group C2/c with a = 24.249(3), b = 12.069(48), c = 22.7304(08) ?, β = 113.480(7)°, Z = 4, V = 6102(2) ?~3, Dc = 1.462 g·cm~(-3), F(000) = 2728, μ = 1.968 mm~(-1), the final R = 0.0673, w R = 0.1508 and S = 1.085. Its structure can be regarded as a 1-D coordination polymer constructed by Y~(3+) cations, 2,2?-biphenyldicarboxylate, 1,10-phenanthroline and water molecules. The compound not only contains two kinds of organic ligands, but also exhibits interesting wave-like infinite chains and 18-MR windows with the diameter of 4.070(7)? × 5.326(9)?. The structure is further stabilized by means of O–H···O hydrogen bonds and π-π stacking interactions. Furthermore, the luminescent properties(including emission spectrum, CIE chromaticity coordinate and decay curve) of 1 were also investigated in the solid-state at room temperature.     

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.     

A novel one-dimensional organic-inorganic polymer: synthesis and crystal structure of[{Ca(DMF)_5}_2SiMo_(12)O_(40)]_n

A novel polyoxometalate-based organic-inorganic polymer [{Ca(DMF)5}2SiMo12O40]n has been synthesized and characterized by elemental analysis, IR, UV and X-ray single-crystal structural analysis. The title compound crystallizes in a monocline lattice, P21/n, with a =1.3379(3), b = 1.9796(4), c = 1.4574(3) nm, β = 92.24(3)°, V = 3.8568(13) nm3, Z = 2, R1 = 0.083 and Rw = 0.2065. The result of crystal structure analysis indicates that Ca2+ is surrounded by seven coordination oxygen atoms with pentagonal bipyramidal geometry and bridged with terminal oxygen atom of polyanion in the structure. The compound contains an unprecedented one-dimensional linear chain built by alternate polyanions and cationic units through Mo-Od-Ca-O-Ca links in crystal. The IR spectra and X-ray crystallography analysis exhibit that there is a strong interaction between the polyanion and organic group in solid state. The electronic spectra (λ = 200-500 nm) for the title compound dissolved in the mixed solvent of acetonitrile and     

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.