Synthesis, Characterization, and Properties of Supported Tungstozincate Bridged by Co(Ⅱ) Complex Fragment

[CoII(phen)3]2[{(ZnW12O40)CoII(phen)2(H2O)}2CoII(trien)2(NaH2O)2]·3H2O was synthesized via hydrothermal technique and characterized with elemental analyses, IR spectroscopy, TGA-DTA, and variable temperature magnetic susceptibility. The compound crystallized in the monoclinic system with the space group P21/n, a=1.8210 nm, b=2.3592 nm, c=2.2932 nm, β=110.31o, V=9.239 nm3, Z=2, R1=0.0827. The compound consists of two coordination cations, three lattice water molecules, and a macroanion [{(ZnW12O40)Co(phen)2(...     

Synthesis, Crystal Structure and Thermal Stability of Homopolytungstate Supporting Nickel(Ⅱ) Coordination Fragments

The organo-inorganic hybrid compound [ Ni(phen)3 ] [ ( H2W12O40 ) { Ni(phen)2H2O } { Ni(trien) } ]·2H2O was synthesized from Na2WO4·2H2O, NiSO4·6H2O, CH3COOK,triethylenetetramine and 1,10-phenanthroline in water by the hydrothernal reaction, and characterized by IR, X-ray single crystal diffraction, and TG-DTA analysis.This compound crystallized in the monoclinic system, space group P2 ( 1 )/n, with lattice constants: a = 1. 80998 (6) nm, b =2.36504(8) nm, c=2.29199(7) nm, β=110.2220(10)°, V=9.2065(5) nm, Z=4. Final R indices R1 =0.0532, wR2 =0.1295. The compound is decomposed at 593 ℃.     

Synthesis, Crystal Structure and Thermal Stability of Homopolytungstate Supporting Nickel（Ⅱ） Coordination Fragments

The organo-inorganic hybrid compound [Ni(phen)3] [(H2W12O40){Ni(phen)2H2O} {Ni(trien)}]·2H2O was synthesized from Na2WO4·2H2O,NiSO4·6H2O,CH3COOK,triethylenetetramine and 1,10-phenanthroline in water by the hydrothermal reaction,and characterized by IR,X-ray single crystal diffraction,and TG-DTA analysis.This compound crystallized in the monoclinic system,space group P2(1)/n,with lattice constants:a=1.80998(6)nm,b=2.36504(8)nm,c=2.29199(7)nm,β=110.2220(10)°,V=9.2065(5)nm,Z=4.Final R indices R1=0.0532,wR2=0.1295.The compound is decomposed at 593 ℃.     

Synthesis,Characterization, and Properties of Supported Tungstozincate Bridged by Co（Ⅱ） Complex Fragment

[Co^11（phen）3]2[{（ZnW12O40）Co^11（phen）2（H2O）}2Co^11（trien）2（NaH2O）2]·3H2O was synthesized via hydrothermal technique and characterized with elemental analyses, IR spectroscopy, TGA-DTA, and variable temperature magnetic susceptibility. The compound crystallized in the monoclinic system with the space group P21/n, a=1.8210 nm, b=2.3592 nm, c=2.2932 nm, β=110.31°, V=9.239 nm^3, Z=2, R1=0.0827. The compound consists of two coordination cations, three lattice water molecules, and a macroanion [{（ZnW12O40）Co（phen）2（H2O）}2Co（C6H18N4）2·（NaH2O）2]^4- in which each supported Keggin anion [（ZnW12O40Co^11（phen）2（H2O）]^4- acts as a ligand to coordinate to central bridging Co^2＋ ion via a terminal oxygen atom. Hydrogen bonds are responsible for the construction of 3D architecture of the compound. The compound is paramagnetic with a weak antiferromagnetic interaction（0=-46.796 K）.     

Syntheses and Crystal Structures of a Cadmium(Ⅱ) and a Zinc(Ⅱ) Complexes with the Flexible Ligand 1-Acetic Acid-2, 2'-biimidazole

Reactions of NaAcebiim(NaAcebiim = 1-acetic acid-2, 2′-biimidazole monosodium salt) and cadmium or zinc nitrate produce two supramolecular architectures, namely, 1D [Cd(Acebiim)(NO3)(H2O)]n(1) and 0D [Zn(Acebiim)2(H2O)2]·2H2O(2) in acidic aqueous solutions. Single-crystal X-ray diffraction analysis reveals that complex 1 crystallizes in the triclinic system, space group P1, and 2 is of monoclinic system, space group P21/n. In 1, two nitrate groups link two Cd(Ⅱ) ions forming [Cd2(NO3)2(H2O)2] as secondary building units that are interconnected by the Acebiim- ligand into an infinite ladder. In 2, the hydrogen-bonded synthon R22(16) between the N–H moieties and carboxylic acid link [Zn(Acebiim)2(H2O)2], generating a 1D-extended ribbon. Moreover, hydrogen bonds and π-π interactions further stabilize the 3D supramolecular architecture.     

Hydrothermal Synthesis and Crystal Structure of Binuclear Copper(Ⅱ) Complex Bridged by 1,2,4,5-Benzenetetracarboxylato Trivalent Anion

The title complex [(phen)2Cu(Htcb)Cu(phen)2]H3tcb(tcb=1,2,4,5-benzenetetracarboxylato tetravalent anion; phen=1,10-phenanthroline) was synthesized by the hydrothermal synthesis method. The crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in the triclinic system with space group P1, a=1.04174(8) nm, b=1.07119(8) nm, c=1.26360(10) nm, α=98.169(2)°, β=99.679(10)°, γ=93.658(10)°, V=1.37031(18) nm3, Z=1. The two copper(Ⅱ) cations are bridged by Htcb in the monodentate fashion, and have the same five-coordinated environment completed by the four N atoms from the two phen molecules and one O atom from the carboxylic group of Htcb respectively, which can be best described as distorted trigonal-bipyramid geometry. Moreover, the three dimensional network is formed by H-bonding interactions [O…O distance from 0.2506(10) nm to 0.3176(11) nm] and π-π stacking interactions between the phen rings of adjacent binuclear entities with a face-to-face separation of ca. 0.354 nm.     

Cis-and Trans-Coordination Assembly of Nitrogen Heterocycle with Copper(Ⅱ) and Silver(Ⅰ)

After the preparation of 1,4-bis(4,5-dihydro-1H-imidazol-2-yl)benzene(bdib), a nitrogen heterocycle with potential coordination manners of both cis- and trans-configuration forms, three complexes, including cis-[Cu2(bdib)2(μ-OCH3)2]Cl2·2MeOH(1), trans-[Cu(bdib)(AcO)2]n(2), and cis-[Ag2(bdib)2](NO3)2·2H2O(3), were successfully self-assembled. Complexes 1 and 2 crystallized in the monoclinic system with P21/n space group and complex 3 in the triclinic system with Pī space group.     

Hydrothermal Synthesis and Crystal Structure of a Polyoxometalate- based Complex [Cu^I（phen）2]4（SiW12O40）

A new hybrid polyoxometalate-based complex, [Cu^I（phen）214（SiW12O40） （phen = 1,10-phenanthroline）, has been synthesized by hydrothermal method and characterized with the aid of elemental analysis, IR, UV spectra and thermal analysis studies. The result of X-ray crystallography analysis exhibits that the title compound crystallizes in the orthorhombic space group P212121, and the formula is C96H64N16Cu4SiW12O40. Crystal data： a = 18.3574（14）, b = 21.1952（16）, c = 27.992（2）A, Mr = 4570.08, V = 10891.4（14）A^3, Z = 4, Dc = 2.787 g/cm^3,μ = 13.478 mm^-1, R = 0.0364, wR = 0.0638 （I 〉 2σ（I）） and F（000） = 8360. The complex consists of one α-Keggin anion [SIW12O40]^4- and four discrete [Cu^I（phen）2]^＋ cations. The valence sum calculations for the Cu atoms suggest that all four Cu atoms are in the ＋1 oxidation state.     

The structure-directing effect of n-propylamine in the crystallization of open-framework aluminophosphates

Using n-propylamine as a template,deioned water and secondary-butanol(butan-2-ol)as solvents,a three-dimensional(3D)open-framework aluminophosphate[C3NH10]·[HAl3P3O13](1)and a two-dimensional layered aluminophosphate[C3NH10]3·[Al3P4O16](2)were crystallized from the initial mixtures with compositions of Al2O3:2.4 P2O5:5.0 n-propylamine:100 H2O/butan-2-ol,respectively.They are characterized by X-ray powder diffraction(XRD),thermogravimetric(TG),and elemental(CHN)analyses and structurally determined by single-crystal X-ray diffraction analysis.Compound 1 crystallizes in the monoclinic space group P21/c with a=0.85831(13)nm,b=1.7677(3)nm,c=1.04353(12)nm,=123.887(9)°,and V=1.3143(3)nm3.Compound 2 crystallizes in the monoclinic space group P21/c with a=1.1313(2)nm,b=1.4874(3)nm,c=1.8020(6)nm,=125.07(2)°,and V=2.4817(11)nm3.The results show that the properties of solvent have a significant influence on the structure-directing effect of n-propylamine in the crystallization of the open-framework aluminophosphates.     

Two Zinc（Ⅱ） Carboxyarylphosphonates with Unusual Polynuclear Zn（Ⅱ） Units：Syntheses and Crystal Structures

[Zn2(PCP)(phen)(H2O)F]n 1 and {[Zn3(MCP)2(phen)2(H2O)]·2.5H2O}n 2(PCP = p-O2C(C6H4)PO33-,MCP = m-O2C(C6H4)PO33- and phen = phenanthroline) were obtained by hydrothermal synthesis and characterized by X-ray single-crystal diffraction.Compound 1 crystallizes in the monoclinic P21/c space group with a = 7.908(2),b = 20.254(3),c = 13.477(2) ,β = 107.76(3)°,V = 2055.7(8) 3,Z = 4,C20H16FN2O6PZn2,Mr = 561.10,Dc = 1.813 g/cm3,μ = 2.463 mm-1,F(000) = 1128,the final R = 0.0340 and wR = 0.0794.Compound 2 crystallizes in the monoclinic P21/n space group with a = 15.629(3),b = 18.141(4),c = 17.723(7) ,β = 121.89(2)°,V = 4267(2) 3,Z = 4,C40H31N4O13.5P2Zn3,Mr = 1041.70,Dc = 1.620 g/cm3,μ = 1.818 mm-1,F(000) = 2108,the final R = 0.0669 and wR = 0.1775.In compound 1,the tetranuclear Zn4 units are linked together by μ4-PCP3- to build 2D(4,4) layers,which are further interconnected through the μ2-bridging fluorion into a 3D framework with 1D phen ligands-filled channels.As for the 3D supramolecular framework of 2,the novel hexanuclear Zn6 units with "chair" conformation are extended by the moieties of μ4-MCP3- ligand to a 2D(4,4) layer on the bc plane,which is viewed as the 2-folded layers in 1.In both compounds,the structures are stabilized by hydrogen bonding interactions and π-π stacking interactions between the phen rings.Additionally,FT-IR spectroscopy and the fluorescent properties are discussed.     

Synthesis, Crystal Structure and Photocatalytic Properties of a Supramolecular Assembly Based on Keggin Polyoxotungstate

A new supramolecular compound (4,4'-bipyH)4[SiW12O40](4,4'-bipy) (4,4'-bipy = 4,4'-bipyridine) was synthesized hydrothermally and characterized by single-crystal X-ray diffraction and IR spectrum. The crystallography analysis for the title compound reveals that the crystal crystallizes in monoclinic, space group C2/m with a = 22.2767(12), b = 21.1879(11), c = 15.6942(8) , β = 97.068(3)°, V = 7351.3(7) 3, C50H44N10O40SiW12, Mr = 3659.24, Z = 4, Dc = 3.306 g/cm3, F(000) = 6544, GOOF = 1.137, R = 0.0577 and wR = 0.1579. The title compound consists of a discrete Keggin-type [SiW12O40]4- anion, one 4,4'-bipy and four protonated (4,4'-bipyH)+ cations. The [SiW12O40]4- anion and protonated 4,4'-bipy are connected to form a supramolecular structure by hydrogen bonds. Meanwhile, the title compound exhibits good photocatalytic activity for color degradation of Rhodamine-B dye solution under visible-light irradiation.     

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.     

Two Ion-pair Complexes Constructed by[M（mnt）2]n- （M=Ni,Co,mnt = Maleonitriledithiolate）:Syntheses,Characterization and Thermal Stability

Two new ion-pair complexes [Co(BBP)2]2[Ni(mnt)2]Cl2·4DMF·2H2O(1, BBP =2,6-bis(benzimidazol-2'-yl) pyridine, mnt = maleonitriledithiolate) and [(Py)2CH2][Co(mnt)2]2·4DMF(2) have been synthesized and characterized by elemental analyses, IR spectroscopy,thermogravimetric analyses and single-crystal X-ray diffraction. X-ray diffraction studies show that complex 1 crystallizes in monoclinic, space group P21/c. The crystal of 2 belongs to a triclinic system with space group P1. Due to the hydrogen bonding interactions, anions and cations formed the mixed packing in complex 1 while the anions and cations formed segregated columns in 2. In addition, thermogravimetric analyses of the two complexes are also investigated.     

Three 3D M~Ⅱ (M = Co,Ni, Zn) Supramolecular Polymers Constructed from O-vanillic Acid: Synthesis,Crystal Structure and TGA

The title compounds, [Co(H2O)6](OVA)2·2H2O 1, [Ni(H2O)6](OVA)2·2H2O 2 and [Zn(OVA)2·2H2O] 3 (HOVA = o-vanillic acid = 2-hydroxy-3-methoxybenzoate), were synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR and TGA. Compounds 1 and 2 are both of triclinic with space group P1. The metal atom coordinated by six water molecules displays a slightly distorted octahedral configuration. Interestingly, the carboxyl group from HOVA ligand does not coordinate to the metal atom. Correspondingly, compound 3 belongs to the monoclinic system, space group C2/c. Each zinc(Ⅱ) atom exhibits a distorted four-coordinated tetrahedral geometry. Two monodentate carboxyl groups link one zinc(Ⅱ) atom to form a mononuclear molecule. The structure feature is different from that of compounds 1 and 2, which could be attributed to the different coordinated numbers and radii of Co(Ⅱ), Ni(Ⅱ) and Zn(Ⅱ) atoms.     

Hydrothermal Syntheses,Crystal Structures and Luminescence Properties of Cu(Ⅱ) and Cd(Ⅱ) Complexes Assembled by 6-Hydroxypicolinic Acid and 1,10-Phenanthroline

Two new complexes based on 6-hydroxypicolinic acid(H_2picO) and 1,10-phenanthroline(phen), such as [Cu_4(picO)_4(phen)_4]·12 H_2O(1) and {[Cd_4(picO)_4(phen)_4(H_2O)_2]·5H_2O}_n(2), have been synthesized and characterized by IR, elemental analyses, thermogravimetric analyses and X-ray diffraction technique. Single-crystal X-ray diffraction analyses revealed that the two complexes both crystallize in the triclinic system, space group P(16)-. For complex 1, the picO ligands adopt a tridentate coordination mode to link copper(Ⅱ) ions into dimmers. PicO ligands also adopt a tridentate mode in complex 2, which connects the cadmium(Ⅱ) to form a one-dimensional chain. Moreover, luminescent properties of 1 and 2 were also investigated.     

A Novel Dimer--Heteropolytungstate with a Vanadium Atom as the Centre--Synthesis and Structural Characterization of (H3O)4[VW12O40Na(H2O)4]2

A novel dimer-tungstovanadate,(H3O)4［VW12O40Na(H2O)4］2,was hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction,IR spectra,TGA-DSC thermal analysis and polarograpy.The yellowish crystal crystallized in the triclinic system,space group ,a=1.464 5(3) nm,b=1.4686(3) nm,c=1.4111(3) nm,α=111.82(2)°,βA novel dimer-tungstovanadate,(H3O)4［VW12O40Na(H2O)4］2,was hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction,IR spectra,TGA-DSC thermal analysis and polarograpy.The yellowish crystal crystallized in the triclinic system,space group ,a=1.464 5(3) nm,b=1.4686(3) nm,c=1.4111(3) nm,α=111.82(2)°,β=93.17(3)°,γ=117.47(3)°,V=2.2106(8) nm3,Z=1,Dc=4.552 g.cm-3,λ(Mo Kα)=0.071073 nm,μ=31.402 mm-1,F(000)=2648,R=0.0780.The title compound consists of two Keggin structure units linked together with two hydrated sodium cations to form a dimer with a porous structure with the pore dimension of 0.766 nm×0.7785 nm.     

Heterometallic Trinuclear Ni2Zn and Ni2Mn Complexes of Macrocyclic Oxamide: Synthesis and Crystal Structures

Two novel heterometallic trinuclear complexes of macrocyclic oxamide [Mn(NiL)2(HBTC)H2O] (1) and [Zn(NiL)2(HBTC)H2O] (2) (NiL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H3BTC = 1,3,5-benzenetricarboxylic acid) have been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. For 1, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.3595(5), b = 23.1498(11), c = 17.2558(8) and =101.2530(10)°. For 2, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.5214(8), b = 20.6566(14), c = 18.4126(13)  and = 92.6770(10)°. The structures of 1 and 2 have oxamido-bridged trinuclear [NiⅡ2MⅡ] units and consist of two-dimensional supramolecular architectures formed by strong O-H…O intermolecular hydrogen bonds.     

Synthesis,crystal structure and characterization of a 2-D network organic-inorganic hybrid polymer with α-BW_(12)O_(40) ~(5-) as building blocks

A two-dimensional network compound [Ce(DMF)4(H2O)][α-BW12O40]·H2O·(HDMA)2 (HDMA = protoned dimethylamine, DMF = N,N-dimethylformamide) was synthesized from α-H5BW12O40·nH2O, Ce(NO3)3·6H2O and DMF and characterized by IR, UV spectra and TG-DTA. The result of the X-ray single crystal diffraction indicates that the crystal is monoclinic, space group P21/n, with unit cell dimensional: a = 1.1983(3), b = 2.4216(5), c = 1.9517(4) nm, β = 92.91(3)°, Z = 4, R1 = 0.07710, wR2 = 0.1416. Structural analysis indicates that every [Ce(DMF)4(H2O)]3 building block is surrounded by three adjacent [α-BW12O40]5- polyanions, meanwhile, every [α-BW12O40]5- polyanion interconnects with three neighboring [Ce(DMF)4(H2O)]3 subunits, by making use of which two-dimensional network structure can be constructed. The result of thermogravimetric analysis manifests that the title compound has two-stage weight loss and the decomposition temperature of the title polyanionic framework is 560℃ . The electrochemical analysis shows the title polyanion has three-step redox processes in the pH = 4―7 media.     

Synthesis,Crystal Structure and Spectroscopic Properties of Zn(Ⅱ) with N-carbamylglutamate Ligand

Zn C6H8N2O5.H2O(NCGZn) has been synthesized, and its functional groups present in the title compound were confirmed by elemental analysis, TG and IR spectral studies. Meanwhile, the crystal of NCGZn was obtained by slow evaporation of a saturated aqueous solution at room temperature and confirmed by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P21 with a = 5.03220(1), b = 13.3747(4), c = 12.9944(4) , β = 92.987(2)o, V = 873.39(4) 3, Z = 2, C12H20N4O12Zn2, Mr = 543.10, Dc = 2.065 g/cm3, F(000) = 552, μ(Mo Ka) = 2.826 mm-1, R = 0.0422 and w R = 0.1142. In NCGZn, Zn(1) and the symmetry formed Zn(1) ions are connected by five atoms from four NCG-2H anions and a water molecule. A NCG ligand has two carboxylate groups, one connecting a Zn ion, and the other bridgiong two Zn ions. The NCG ligand bridges four Zn ions through the amino group and two carboxylate groups with a water molecule to yield a 3D coordination polymer structure with hydrogen bonds.     

Synthesis and Crystal Structures of Two Di-Cu(Ⅱ) Complexes Based on an Asymmetric Dinucleating Ligand

Two new dicopper(II) complexes [Cu2L(OAc)2](ClO4)·H2O(1) and [Cu2L(BPP)2]-(ClO4)(2) using an asymmetric dinucleating ligand HL and auxiliary ligands such as acetate(OAc) and bisphenyl phosphate(BPP) have been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Complex 1 crystallizes as blue single crystals that belong to the triclinic crystal system and P1 space group, while complex 2 crystallizes in a monoclinic P21/c space group. Single-crystal X-ray diffraction analysis reveals that the two copper ions in complexes 1 and 2 reside within the adjacent ligand compartments and are bridged by the endogenous phenoxo-O from ligand L and the introduction of two desired exogenous carboxylates or phosphates in the bidentate μ-1,3-bridged mode. The coordination geometries of Cu(1) and Cu(2) are both distorted square pyramids.