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(...     

Imidazole Coordinated Sandwich-type Antimony Polyoxotungstates Na9[ {Na（H=O2}3{M（C3H4N2）}3（ Sb W9O33）2]·xH=O（M=Ni^Ⅱ, Co^Ⅱ, Zn^Ⅱ, Mn^Ⅱ）

The imidazole covalently coordinated sandwich-type heteropolymngstates Na9[ {Na（H=O2}3{M（C3H4N2）}3（ Sb W9O33）2]·xH=O（M=Ni^Ⅱ, Co^Ⅱ, Zn^Ⅱ, Mn^Ⅱ） were obtained by the reaction of Na2WO4·2H2O, SbCl3·6H2O, NiCl2·6H2O [MnSO4·H2O, Co（NO3）2·6H2O, ZnSO4·7H2O] and imidazole at pH≈7.5. The structure of Na9[{Na（H2O）2}3{Ni（C3H4N2）}3（SbW9O33）2]·32H2O was determined by single crystal X-ray diffraction. Polyanion [{Na（H2O）2}3{Ni（C3H4N2）}3（SbW9O33）2}3]^9- has approximate C3v symmetry, imidazole coordinated six-nuclear duster [{Na（H2O）2}3{Ni（C3H4N2）}3]^9＋ is encapsulated between two （α-SbW9O33）^9-, the three rings of imidazole in the polyanion are perpendicular to the horizontal plane formed by six metals （Na-Ni-Na-Ni-Na-Ni） in the central belt, and x-stacking interactions exist between imidazoles of neighboring polyanions with dihedral angel of 60%. The compounds were also characterized by IR, UV-Vis spectra, TG and DSC, and the thermal decomposition mechanism of the four compounds was suggested by TG curves.     

Synthesis and Crystal Structure of a New Complex {[ Co^ⅢL2]·[Co^Ⅱ（H2O）6]0.6·2.25H2O }4 （H2L = N-（2-Hydroxyphenyl）salicylidenimine）

The reaction of Co（OAc）2·4H2O with the Schiff base H2L in a methanol solution affords the red crystals of { [Co^ⅢL2]·[Co^Ⅱ（H2O）6]0.5·2.25H2O}4 1 （H2L = N-（2-hydroxyphenyl） salicylidenimine）. The molecular and crystal structures were determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n, C104Hi14Co6NaO37, Mr = 2421.61, a = 10.625（3）, b = 16.335（4）, c = 15.265（4）A^°, β = 102.990（4）°, V= 2581.6（11）A^°^3, Z = 1, Dc= 1.558 g/cm^3,μ = 1.034 mm^-1, F（000） = 1252, R = 0.0414 and wR = 0.1167 for 5889 reflections. The Co（HI） atom is six-coordinated by two nitrogen atoms and four oxygen atoms of two tridentate L ligands. The abundant hydrogen bonding interactions extend the complex into a one-dimensional supra- molecular framework. The uncoordinated water molecules act as space-fillers and consolidate the whole architecture through the hydrogen bonding interactions.     

Hydrothermal synthesis, structure and quantum chemistry of transition metal complex supported by metal-oxo cluster[{Ni(phen)_2}_2(ξ-Mo_8O_(26))]

A nickel-1,10-phenanthroline complex supported on an octamolybdate, [{Ni(phen)2}2(ξ-Mo8O26)], has been hydrothermally synthesized with MoO3, H2MoO4, Ni(OAc)2 · 6H2O and 1,10-phenathroline (1,10-phen) as raw materials. The crystals of the compound belong to mono-clinic P21/n space group, a= 1.2952(2), b = 1.6659(10), c= 1.3956(12) nm, β=106.273(8)°, V = 2.8906(5) nm3, Z = 2. 5604 observable reflections (/>2σ(/)) were used for structure resolution and refinements to converge to final R1 = 0.0414, wR2 = 0.0815. The result of structure determination shows that the compound contains octamolybdate possessing a novel structure type (named as ξ-isomer). The feature of ξ-[Mo8O26]4- is that it is composed of Mo6O6 ring and two MoO6 octa-hedra located at cap positions on opposite faces. The Mo6O6 ring contains two octahedral and four trigonal-bipyramidal MovI atoms. Each ξ-[Mo8O26]4- unit is bonded with two [Ni(phen)2]2+ through terminal oxygen atoms of octahedral and neighbouring trigonal-bipyramidal Mo at     

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 ℃.     

二个钴5-磺酸基水杨酸、邻菲罗啉配合物的合成、次级合成与结构

Cobait（Ⅱ） nitrate reacted with 1,10-phenanthroline （phen） and 5-sulfosaiicylic acid （H3ssal） to yield the cobait（Ⅰ） complex [Co（phen）2（H2O）2]（Hssal）o4H2O （1） and the reaction of 1 with copper acetate led to a novel complex [Co（phen）（H2O）4][Cu2（ssal）2（phen）2]·5H2O （2）. These two complexes were cationanion species and the cationic motif [Co（phen）2（H2O）2]^2＋of 1 could be converted to [Co（phen）（H2O）4]^2＋ in the formation process of new anion [Cu2（phen）2（ssal）2]^2- of 2. In both complexes abundant hydrogen bonds construct different supramolecular architectures, thus the conversion reaction can provide a new path to create novel supramolecular network.     

Syntheses,Structures, and Properties of Three Coordiantion Polymers： [Cd2（bpp）1.5（Hbpp）（phen）2]n, [Mn3（Htptc）2（phen）2（H2O）2]n,and {[Cu（btc）0.5（1,4-bib）]？2H2O}nSyntheses,Structures, and Properties of Three Coordiantion Polymers： [Cd2（bpp）1.5（Hbpp）（phen）2]n, [Mn3（Htptc）2（phen）2（H2O）2]n,and {[Cu（btc）0.5（1,4-bib）]？2H2O}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＇-tetracar- boxylic 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 single- crystal 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）2（43.62.8）（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.     

Synthesis,Crystal structure and Luminescent Property of a New 3D Supramolecular Compound （C6H6NO2）3（C6H5NO2）（PW12O40）·2H2O

A supramolecular compound （C6H6NO2）3（C6H5NO2）（PW12O40）·2H2O including the Keggin-type [PW1O40]3- polyanion, [HC6H5NO2]＋ （protonated pyridine-4-carboxylic acid molecule）, C6H5NO2 （pyridine-4-carboxylic acid molecule） and two free H20 molecules has been synthesized by the hydrothermal method and characterized by elemental analysis, IR spectra, single-crystal X-ray diffraction and powder X-ray diffraction. The crystal belongs to orthorhombic, space group Pnnm with a = 1.0483（3）, b = 1.4368（6）, c = 2.0526（7） nm, V= 3.0918（18） nm3,Z = 2, F（000） = 3004, Mr= 3406.07, Dc= 1.757 g.m-3,μ = 41.241 mm-1, the final R = 0.0387 and wR = 0.1089 for 2091 observed reflections withI〉 2σ（I）. A total of 30431 reflections were collected, of which 3083 were independent （Rint = 0.0605）. S is 1.182. The title compound presents a 3-D structure via intermolecular hydrogen bonds among [PW12O40]3- polyanions and pyridine-4-carboxylic acid ligands. The ultraviolet and luminescence spectra have been studied at room temperature, of which the purple fluorescent emission is located at 363 nm when excited at 264 nm. Fluorescent emission of the compound derives from the π-π＊ transitions in the pyridine-4-carboxylic acid ligands.     

Synthesis and Structure of a New Mixed-polyoxometalate （W/Mo） Compound： H5K{[Co（H2O）5]2（H2Mo3.24W8.76O42）}·19H2O

One new polyoxometalate compound connected via cobalt/potassium cations,namely H5K{[Co（H2O）5]2（H2Mo3.24W8.76O42）}·19H2O 1,was prepared and characterized by ele- mental analysis and IR spectroscopy. Single-crystal X-ray diffraction analysis result reveals that anions of {[Co（H2O）5]2（H2Mo3.24W8.76O42）}6- in compound 1 are linked by potassium cations to form one- dimensional chain,based on which a three-dimensional network is further constructed with the help of hydrogen bonds. Crystal data： H67Co2KMo3.24O72W8.76,Mr = 3297.87,monoclinic,C2/c,a = 19.0126（10）,b = 16.6025（5）,c = 19.1908（10）A,β = 106.713（1）°,V = 5801.8（5） A^3,Z = 4,Dc = 3.755 g/cm^3,F（000） = 5961,μ = 18.730 mm^-1,R = 0.0569 and wR = 0.1437 （I 〉 2σ（I））.     

{Mo102}型纳米多孔无机富勒烯衍生物的合成、表征及三阶非线性光学性质

在室温酸性条件下, 利用高负电性的表面分布有20个{Mo9O9}型纳米孔道的无机富勒烯囊状阴离子[{(MoⅥ)Mo5ⅥO21(H2O)6}12{Mo2ⅤO4(SO4)}30]72-与胍基乙酸反应, 得到了表面分布有20个{Mo6O6}型纳米孔道的由102个Mo及氧原子组成的[{(Mo)Mo5O21(H2O)4SO4}12{MoⅤO(H2O)}30]12-小无机富勒烯囊状阴离子. 通过单晶X射线衍射、元素分析、FTIR、UV-Vis、TG-DTA、ESR等手段对其进行了表征. 该化合物属于三斜晶系, P1空间群, 晶胞参数a=2.5377(5) nm, b=2.5932(5) nm, c=3.9547(8) nm, α =83.58(3) °, β=86.15(3) °, γ=75.55(3) °, V=25.023(9) nm3. 利用脉冲时间为5 ns的532 nm激光通过Z-扫描实验得到该化合物的三阶非线性折射率γ=-3.29×10-18 m2/W, 三阶非线性极化率χ(3)=-1.04×10-23 m2·V-2, 表明该化合物具有较强的自散焦三阶非线性光学效应.     

[Co（phen）3]2[PMo12O40]（OH）的水热合成及晶体结构

利用水热合成法制备了Keggin结构阴离子有机一无机复合物[Co（phen）3]2[PMo12O40]（OH）,通过元素分析,红外光谱和X射线单晶衍射等对其进行了表征．结果表明,该化合物属于单斜晶系,C2／c空间群．=1．97225（18）nm,b=1．81079（16）nm,c=2．5117（2）nm,β=100．5380（10）°,V=8．819O（14）nm^3,Z=4,R1=0．0587,wR2=0．1211．该化合物分子由一个多阴离子[PMo12O40]^3-,两个[Co（phen）3]^2＋及一个羟基组成．     

Synthesis of diamondoid lanthanide-polyoxometalate solids as tunable photoluminescent materials

The reaction between polyoxometalate (POM) [TBA](12)[WZn{Zn(H(2)O)}(2)(ZnW(9)O(34))(2)] (TBA = tetrabutyl ammonium) and lanthanide (Ln) nitrate (Ln = La, Eu and Tb) in a mixed solvent of CH(3)CN and DMF yielded three noncentrosymmetric diamondoid Ln-POM solid materials, {[Ln(2)(DMF)(8)(H(2)O)(6)][ZnW(12)O(40)]}·4DMF (Ln-POM; Ln = La, Eu and Tb). In these compounds, the {ZnW(12)O(40)} unit, transferred from the metastable [WZn{Zn(H(2)O)}(2)(ZnW(9)O(34))(2)] cluster, acts as a tetradentate ligand to connect with four Ln nodes, while the Ln ion links up two {ZnW(12)O(40)} units. These compounds generated interesting luminescence emissions that are dependent on the Ln ions and their ratios. White light emission was obtained by a doped approach with a rational ratio of the Eu(3+) and Tb(3+) ions.     

A novel heterogeneous Co(II)-Fenton-like catalyst for efficient photodegradation by visible light over extended pH

Science China Chemistry - A novel CoII-Fenton-like heterogeneous catalyst, (H3O)2[CoII(phen)(H2O)2]2[MoVI5O15(PO4)2]·4H2O (phen=1,10-phenanthroline, C12N2H8) (1), is synthesized and utilized...     

Magnetism in polyoxometalates: anisotropic exchange interactions in the Co3II moiety of [Co3W(D2O)2(ZnW9O34)2](12-)--A magnetic and inelastic neutron scattering study

The ground-state properties of a Co3II moiety encapsulated in a polyoxometalate anion were investigated by combining measurements of specific heat, magnetic susceptibility, and low-temperature magnetization with a detailed inelastic neutron scattering (INS) study on a fully deuterated polycrystalline sample of Na12[Co3W(D2O)2(ZnW9O34)2].40D2O (Co3). The ferromagnetic Co3O14 cluster core consists of three octahedrally oxo-coordinated CoII ions. According to the single-ion anisotropy and spin-orbit coupling of the octahedral CoII ions, the appropriate exchange Hamiltonian to describe the ground-state properties of the Co3 spin cluster is anisotropic and is expressed as H = -2 sigma a = x,y,z (Ja12 S1a S2a + Ja23 S2a S3a), where Ja are the components of the exchange interactions between the CoII ions. To reproduce the INS data, different orientations of the two anisotropic J tensors must be considered, and the following conditions had to be introduced: Jx12 = Jy23, Jy12 = Jx23, Jz12 = Jz23. This result was correlated with the molecular symmetry of the complex. The following set of parameters was obtained: Jx12 = Jy23 = 1.37, Jy12 = Jx23 = 0.218, and Jz12 = Jz23 = 1.24 meV. This set also reproduces in a satisfactory manner the specific heat, susceptibility, and magnetization properties of Co3.     

Hydrothermal Synthesis and Crystal Structure of a Keggin Polyoxometalate [CoⅡ(2,2'-bipy)2(H2O)]2[SiWVI12O40]·2H2O

A Keggin-type tungstosilicate compound [CoII(2,2'-bipy)2(H2O)]2[SiWVI12O40]·2H2O1 (bipy = bipyridine) was prepared by a hydrothermal method for the first time. Single-crystal X-ray diffraction revealed that 1 (C4H40Co2N8O44SiW12) crystallizes in the triclinic system, space group P1 with a = 10.4979(6), b = 13.3946(7), c = 13.5756(8) (A°), α= 70.0769(18), β= 68.910(3), y = 74.186(4)°,V =1649.84(16) (A°)3, M, = 3688.95, Z =1, Dc= 3.713 mg.m-3,μ= 21.432 mm-1, F(000) = 1644, S =1.058, the final R = 0.0511 and wR = 0.1023 for 6523 observed reflections (I> 2σ(I)). Compound 1 consists of two coordinated cation fragments [CoII(2,2'-bipy)2(H2O)]2+, one normal Keggin polyanion unit [SiWVI12O40]4- and two lattice water molecules. To be noted, each polyanion unit is linked to two cation fragments by its two surface terminal oxygen atoms and two cobalt atoms of two cation fragments forming an organic-inorganic hybrid unit in 1. Furthermore, the compound shows strong photo-luminescence property in the solid state at room temperature.     

Photoinduced magnetization with a high curie temperature and a large coercive field in a cyano-bridged cobalt-tungstate bimetallic assembly

A three-dimensional magnetic material [{CoII(pyrimidine)(H2O)}2{CoII(H2O)2}{WV(CN)8}2](pyrimidine)2. 2H2O is prepared. This compound exhibits a charge-transfer-induced spin transition with a large thermal hysteresis loop of 90 K. Irradiating with light causes the low-temperature phase to exhibit a spontaneous magnetization with a Curie temperature of 40 K and a magnetic hysteresis loop with a coercive field of 12 000 G, which is the highest value reported for a photomagnet. The observed photoinduced magnetization is due to the charge-transfer phase transition from the {CoIIhs(S = 3/2)}{CoIIIls(S = 0)}2-NC-{WIV(S = 0)}2 phase to the {CoIIhs(S = 3/2)}3-NC-{WV(S = 1/2)}2 phase by the irradiation.     

以邻菲咯啉及均苯三甲酸为配体的钴(Ⅱ)配合物的合成、晶体结构及性质研究

采用水热条件合成了1个钴配合物[Co(phen)(HBTC)(H2O)3].2.5H2O(phen=1,10-邻菲罗啉,H3BTC=均苯三甲酸),通过元素分析,红外光谱,紫外光谱,热重分析对其结构和性质进行表征及研究,用X-射线单晶衍射测定了该化合物的晶体结构。晶体属于单斜晶系,空间群为P21/n,晶胞参数a=0.78889(8)nm,b=1.9000(2)nm,c=1.56387(16)nm,β=98.780(2)°,V=2.3166(4)nm3,Z=4。标题化合物的不对称单元由1个配合物分子[Co(phen)(HBTC)(H2O)3]及2.5个结晶水分子组成,氢键将它们连接起来,形成了三维网络结构。利用循环伏安法测定了配合物的电化学性质,并测定了配合物的荧光光谱,发现配合物在383和469 nm两处有发射峰。     

Hydrothermal Synthesis and Crystal Structure of a Keggin Polyoxometalate [Co^Ⅱ（2,2′-bipy）2（H2O）]2[SiW^Ⅵ12O40]·2H2O

A Keggin-type tungstosilicate compound [Co^Ⅱ（2,2′-bipy）2（H2O）]2[SiW^Ⅵ12O40]·2H2O 1 （bipy = bipyridine） was prepared by a hydrothermal method for the first time. Single-crystal X-ray diffraction revealed that 1 （C40H40Co2N8O44SiW12） crystallizes in the triclinic system, space group P1 with a = 10.4979（6）, b = 13.3946（7）, c = 13.5756（8）A, α= 70.0769（18）, β = 68.910（3）, γ = 74.186（4）°, V = 1649.84（16）A^3, Mr = 3688.95, Z = 1, Dc = 3.713 mg·m^-3, μ = 21.432 mm^-1, F（000） = 1644, S = 1.058, the final R = 0.0511 and wR =0.1023 for 6523 observed reflections （I 〉 2σ（I））. Compound 1 consists of two coordinated cation fragments [Co^Ⅱ（2,2′-bipy）2（H2O）]^2＋, one normal Keggin polyanion unit [SiW^Ⅵ12O40]^4- and two lattice water molecules. To be noted, each polyanion unit is linked to two cation fragments by its two surface terminal oxygen atoms and two cobalt atoms of two cation fragments forming an organic-inorganic hybrid unit in 1. Furthermore, the compound shows strong photoluminescence property in the solid state at room temperature.     

含混合配体多酸超分子化合物的水热合成、晶体结构及催化活性

在水热条件下合成了四个含混合配体4,4’-bipy和2,2’-bipy/phen的多酸配位聚合物[Cu(4,4’-bipy)(2,2’-bipy)2]2[SiW12O40]?4H2O (1),[Ag4(4,4’-bipy)3(2,2’-bipy)2][SiW12O40]?2H2O (2),[Cu(4,4’-bipy)(phen)]2[H3O]2[SiW12O40]?8H2O (3)和[Cu(4,4’-bipy-Cl)(phen)]2[H3O][PW12O40]?H2O (4) (bipy = 联吡啶,phen = 邻菲罗啉),通过红外光谱、热重、元素分析、X-单晶衍射对聚合物进行了表征,在苯乙烯催化环氧化反应中,3和4显示了较高的催化活性,这与结构中存在配位不饱和金属中心有关.