A 3D Ba(Ⅱ) Inorganic-organic Hybrid Framework Based on 1,3,5-Benzenetricarboxylic Acid Ligand: Synthesis and Characterization

A three-dimensional(3D) barium complex with 1,3,5-benzenetricarboxylic acid(H3BTC), {[Ba1.5(BTC)(H2O)]·(H2O)}n(1), was synthesized in DMF/EtOH/H2 O mixed solution under solvothermal conditions, and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, thermogravimetric analyses, and photoluminescence measurement. In complex 1, the 2D I2O0 type inorganic layer is constructed by {Ba1O10} and {Ba2O9} polyhedra. Moreover, the solid-state fluorescence measurement reveals a fluorescence emission band at 465 nm under 344 nm excitation, assigned to a charge-transfer transition.     

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,Crystal Structure and Luminescent Properties of a Novel Mn(Ⅱ) Coordination Polymer Based on 1,3,5-Benzenetricarboxylic Acid

Coordination polymers are a novel class of crystalline materials, which have attracted a huge amount of interest in recent decades. We selected an organic ligand 1,3,5-benzenetricarboxylic acid(H_3 BTC) to assemble with Mn(Ⅱ) ions to construct a novel Mn(Ⅱ) coordination polymer crystal material(namely complex 1). The resultant sample was successfully synthesized under the solvothermal reaction. Complex 1 possesses a three-dimensional(3D) framework based on two different Mn(Ⅱ) clusters: [Mn_4(COO)_8] and [Mn_2(COO_4)]. Furthermore, the resultant sample can be characterized in detail by powder X-ray diffraction(PXRD), Fourier-transform infrared spectra(FT-IR), thermal gravimetric analyses(TGA), elemental analysis(C, H and N) and luminescence.     

Hydrothermal Syntheses and Crystal Structures of Six Complexes Constructed from 1,3,5-Benzenetricarboxylic Acid and 4?-(4-Pyridyl)-2,2?:6?,2??-terpyridine Mixed Ligands

Six new transition metal complexes, [Zn(HBTC)(PYTPY)]_n·n PYTPY(1), [Cu(HBTC)(PYTPY)]_n·n PYTPY(2), [Co(HBTC)(PYTPY)]_n·n DMF(3), [Mn(HBTC)(PYTPY)]_n·n DMF(4), [Cd(HBTC)(PYTPY)(H2O)]_n·2nH_2O(5), and [Co(HBTC)(PYTPY)(H_2O)_2](6),(H_3BTC = 1,3,5-benzenetricarboxylic acid, PYTPY = 4?-(4-pyridyl)-2,2?:6?,2??-terpyridine, DMF = N,N?-dimethylformamide), have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complexes 1~5 all feature one-dimensional chain structures, and complex 6 exhibits a zero-dimensional structure. Complexes 1~5 present three-dimensional(3D) supramolecular frameworks via π-π stacking interactions, whenas 6 has also a 3D supramolecular structure assembled by hydrogen bonding. Meanwhile, complexes 1 ~ 6 exhibit the thermal stabilities and photoluminescent properties.     

Simple Preparation,Structure and Conductivity of Nickel(Ⅱ) Benzenetricarboxylate Ni_3(BTC)_2·12H_2O

Proton-conductive crystalline metal-organic framework nickel(Ⅱ) benzenetricarboxylate Ni3(BTC)2·12H2O(MOF-Ni) was prepared by the reaction of nickel(Ⅱ) nitrate and 1,3,5-benzenetricarboxylic(BTC) acid in a mixed solvent of N,N-dimethylformamide(DMF)/C2H5OH/ H2O(1:1:1, ν/ν) at low temperature and short reaction time. It was characterized by thermogravimetric analyses(TG), FT-IR and N2 adsorption-desorption. Single-crystal X-ray diffraction analysis indicated that the complex belongs to monoclinic system, space group C2 with a = 17.407(6), b = 12.878(5), c = 6.542(2) , β = 112.07°, V = 1359.0(8)3, Dc = 1.971 g/cm3, μ = 2.166 mm-1 and Z = 2. Linear polarization resistance(LPR) analysis showed that the complex possesses semiconducting properties.     

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.     

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.     

Solvothermal Synthesis, Crystal Structure and Luminescent Property of a Dy（Ⅲ） Coordination Polymer Constructed by 1,2,4,5-Benzenetetracarboxylic Acid

A three-dimensional coordination polymer {[Dy(H2btec)2/4(btec)3/6(H2O)]·2H2O} n has been synthesized through the reaction of DyCl3·6H2O and 1,2,4,5-benzenetetracarboxylic acid by solvothermal technique, and the crystal structure was determined by X-ray diffraction. The Dy(Ⅲ) coordination polymer crystallizes in monoclinic, space group P21/n with a=10.7063(1), b=7.1491(1), c=17.1197(3), α=90, β=97.10, γ=90°, V=1300.31(3)3 , C10H9DyO11 , Dc=2.389g/cm3 , Z=4, F(000)=892, the final R=0.0165 and wR=0.0448 for I > 2σ(I). The title coordination polymer possesses a three-dimensional framework consisting of nine-coordinate Dy(Ⅲ) centers and two kinds of coordination modes for the 1,2,4,5-benzenetetracarboxylic acid ligands. Every btec4- ligand (deprotonated four protons from 1,2,4,5-benzenetetracarboxylic acid) in the title coordination polymer can clamp three Dy atoms like forceps, which could make the Dy atoms closer in the area of metal-metal interaction. The 3-D framework of the coordination polymer has many channels occupied by the free guest water molecules, and the hydrogen bonds between the coordinated carboxylic groups and guest water molecules could stabilize the crystal structure of the title coordination polymer. In addition, the luminescence properties were also studied.     

Synthesis and Crystal Structure of a Novel Heterometallic Complex with 1,2,4,5-Benzenetetracarboxylic Acid and 1,3,5-Tris（imidazol-1-ylmethyl）-2,4,6-trimethylbenzene

A novel heterometallic complex,[Zn4Ni(OH)2(btec)2(titb)2(H2O)2]·2H2O(1)(H4btec=1,2,4,5-benzenetetracarboxylic acid,titb=1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trime-thylbenzene),has been hydrothermally prepared and characterized by IR spectroscopy,elemental analysis and single-crystal X-ray diffraction.The crystal is of triclinic system,space group P1 with a=10.817(10),b=11.878(11),c=14.569(14),α=71.762(12),β=76.122(13),γ=71.493(13)°,V=1665(3)3,C62H62N12O22Zn4Ni,Mr=1647.43,Dc=1.643 g/cm3,F(000)=842,μ=1.784 mm-1 and Z=1.The final R=0.0531 and wR=0.0890 for 3545 observed reflections(Ⅰ 2σ(Ⅰ)).In the title complex,the btec ligand acts as a five-dentate bridging ligand to link up zinc and nickel atoms into a lamellar framework,which are further interlinked into a 3-D framework via the titb ligands.     

Two Metal Ion-controlled Zn(Ⅱ)/Cd(Ⅱ) Coordination Polymers Based on 1,3,5-Benzenetricarboxylic Acid

Two new coordination polymers {[Zn(Hbtc)(bpyb)]·H_2O}n(1) and {[Cd(Hbtc)-(bpyb)_(1.5)]·0.5 bpyb}_n(2)(H_3btc = 1,3,5-benzenetricarboxylic acid, bpyb = 1,4-bis(4-pyridyl)benzene) have been synthesized under hydrothermal conditions. The two compounds were characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. Compound 1 displays a 2-fold interpenetrating 3D supramolecular architecture through O–H···N/O hydrogen bonds and π-π stacking interactions. Compound 2 exhibits a 2D→3D polycatenated structure, which is further stabilized by O–H···N hydrogen bonds. The results indicate that the metal ion has significant effects on the formation and structure of the resulted coordination polymers. Furthermore, thermal stability and photoluminescent properties of 1 and 2 are also discussed in detail.     

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.     

A New Pillared-layer Framework with Rare Mn（II）-triazole-carboxylate Magnetic Layer Exhibiting an Antiferromagnetic Ordering

A novel pillared-layer framework with a (52.6)(53.63.73.8) Schl fli symbol, [Mn(H2O)(Htrz)(Hbtc)]n (1), was prepared by the reaction of 1,2,4-triazole (Htrz), 1,3,5-benzenetricarboxylic acid (H3 btc), and Mn Ⅱ salt and structurally and magnetically characterized. It crystallizes in the orthorhombic system, space group P212121 with a=7.1618(5), b=9.0356(6), c=10.9740(13) , V=1292.54(15) 3 , D c=1.799 g/cm3 , Mr=350.15, Z=4, F(000)=708, μ=1.064 mm -1 , and the final R=0.0177 and wR=0.0462 for 2273 observed reflections with I > 2σ(I). The unique octahedral Mn Ⅱ ion in 1 is periodically linked into a two-dimensional (2D) magnetic layer by μ2 -N1 , N4 -Htrz and syn, anti-COO of doubly deprotonated Hbtc 2anion, which is further supported by the phenyl backbone of Hbtc 2ligand to generate a 3D pillared-layer framework. Magnetically, complex 1 displays an antiferromagnetic ordering below 5.0 K due to the cooperative antiferromagnetic couplings mediated by the mixed heterobridges within the magnetic layer.     

Synthesis,structure, and magnetism of three manganese-organic framework with PtS topology

Three 3D manganese-organic frameworks, Mn2(BPTC)(DMF)2(H2O)·DMF·3H2O(1), Mn2(BPTC)(bipy)(DMF)·DMF·H2O(2), and Mn2(BPTC)(phen)(DMF)·EtOH(3), have been solvothermally synthesized using 3,3′,5,5′-biphenyltetracarboxylic acid(H4BPTC). All complexes are characterized by PXRD, EA, IR and TG. The results show that they all bear the PtS topology with(42.84)(42.84) for the vertex symbols of the planar and tetrahedral nodes, in which the BPTC ligand is considered as a square-planar 4-connected linker, and every binuclear SBU connected to the four BPTC ligands is simplified into tetrahedral 4-connected nodes. Because the three coordination sites of one metal center of SBU are occupied by the coordinated solvent molecules, complex 1 exhibits low stability. After substituting 2,2′-bipy or 1,10-phen for two coordinated solvent molecules, complexes 2 and 3 display evidently higher structure stability. The magnetism property of complex 2 is also discussed in detail.     

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.     

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.     

Syntheses and Crystal Structures of a Series of Coordination Complexes Derived from the Fluorescein Ligand

Solvothermal reaction of lanthanide(Ⅲ) salts with fluorescein (2-(6-hydroxy3-oxo-3H-xanthen-9-yl)benzoic acid) led to a series of new coordination polymers {[Ln(C 20 H 11 O 5)(C 20 H 10 O 5)(H 2 O)]·DMF} n (Ln=Er,Eu,Gd,Tb,Tm,Yb).The PXRD patterns of the complexes indicate they are isomorphous.The structure of complex {[Er(C 20 H 11 O 5)(C 20 H 10 O 5)(H 2 O)]·DMF} n has been determined by single-crystal X-ray diffraction,revealing a 2D framework in which DMF molecules were filled between the layers.The crystal structure belongs to the triclinic system,space group P1,with a=12.107(4),b=12.232(4),c=13.273(4),α=68.005(7),β=88.024(11),γ=77.451(8)°,V=1776.7(9) 3,Z=2,D c=1.720 g/cm 3,μ=2.434 mm-1,F(000)=918,R int=0.0584,T=293(2) K,the final R=0.0621 and wR=0.1501.     

Isolation of hemoglobin with metal–organic frameworks Y(BTC)(H_2O)_6

The hierarchical metal-organic frameworks(MOFs),such as Y(BTC)(H_2O)_6,are prepared with yttrium nitrate and benzene-1,3,5-tricarboxylic acid at room temperature.The product is characterized by Fourier transform infrared(FT-IR),X-ray diffraction(XRD),scanning electron microscopy(SEM)and thermogravimetric analysis(TGA).The Y(BTC)(H_2O)_6 particles are sufficiently rigid for performing solid phase extraction and they exhibit favorable selectivity toward the adsorption of hemoglobin.The adsorption behavior of hemoglobin onto the Y(BTC)(H_2O)_6 fits the Langmuir adsorption model with a theoretical adsorption capacity of 555.6 mg g 1.An adsorption efficiency of 87.7%for 100μg mL 1hemoglobin in 1 mL sample solution(at pH 6.0)is achieved with 0.40 mg Y(BTC)(H20)6.77.3%of the retained hemoglobin is readily recovered using a 0.5%(m/v)SDS solution as the stripping reagent.Circular dichroism spectra indicated that the conformation of hemoglobin is maintained during the adsorption-desorption process.The MOFs material is applied for the isolation of hemoglobin from human blood and the purity of the obtained hemoglobin is further verified by sodium dodecyl sulfate polyacrylamide gel electrophoresis(SDS-PAGE).     

Syntheses and Anti-lung Cancer Activities of Zn(Ⅱ) and Cu(Ⅱ) Complexes Based on Triazole and Tetrazole,respectively

The reactions of 4H-1,2,4-triazole(Htrz) with ZnCl_2, 1H-tetrazole(Htez) and Cu(NO_3)2·6H_2O afford two novel coordination polymers respectively, {[Zn_2(trz)_2(ox)](H_2O)_3}n(1) and {[Cu_3(tez)_3(OH)_2(H_2O)_2](NO_3)(DMF)_4}_n(2)(H_2ox =(COOH_)2, DMF = N,N-dimethylformamide). 1 shows 1D channels along the a axis filled with water molecules and 2 features a 2D bi-layered framework based on trinuclear Cu(II) units bridged by two μ3-OH groups. In addition, in vitro antitumor activities of compounds 1 and 2 on four human lung cancer cells(16HBE, NCI-H1299, NCI-H460 and NCI-H292) were further determined.     

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.     

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.