三维多酸基无机-有机杂化化合物[Cu_6~Ⅰ(pyz)_6][(PMo_(12)O_(40))_2]·11H_2O的合成、结构及电化学性质

利用水热方法合成了三维多酸基无机-有机杂化化合物[CuⅠ6(pyz)6][(PMo12O40)2]·11H2O(pyz=吡嗪),并通过单晶X射线衍射、红外光谱、元素分析、热重分析和粉末X射线衍射等方法对其进行了表征.结构分析表明该化合物属于立方晶系,Ia-3d空间群,晶胞参数a=b=c=2.602 66(3)nm,α=β=γ=90°,V=17.630 0(4)nm3,Z=8,R1=0.052 7,wR2=0.137 8.进一步研究了该化合物的电化学性质,结果表明其在电催化氧化葡萄糖反应中具有良好的活性.     

Crystal structure and properties of H3[PMo12O40] · 3C2H6O

The title compound H₃[PMo₁₂O₄₀]· 3C₂H₆O was prepared and characterized by X-ray crystallography, its i.r. spectrum, cyclic voltammetry and e.s.r. spectra. The anion of the title compound is a Keggin-type heteropoly structure based upon a central PO₄ tetrahedron surrounded by 12 MoO₆ octahedra arranged in four groups of three edge-shared octahedra Mo₃O₁₃. Weak hydrogen bonds exist between the organic solvent molecules and the heteropoly anion. The catalytic activity of the title compound was determined by the synthesis of butyl acetate. The conversion of n-BuOH reached 93.3% and the yield of MeCO₂Bu-n was 92.0% when the ratio of MeCO₂H to n-BuOH, catalyst amount, reaction time, reaction temperature were 2:1, 0.24% of the reactants (50 mg), 2.0 h and 115 120 °C, respectively.     

超分子化合物(C10N2H9)3[PMo12O40]·3H2O合成与表征

利用水热方法合成了超分子化合物(C10N2H9)3[PMo12O40]·3H2O,通过元素分析、ICP和X射线单晶衍射确定了其晶体结构,并通过IR和XRD进行了结构表征,采用热重分析和循环伏安曲线研究了晶体的热稳定性和氧化还原性．该化合物是由联吡啶、水以及[PMo12O40]3-阴离子组成,它们之间存在较强的氢键作用,自组装成超分子结构化合物．     

有机-无机自由基盐(DBTTF)6PMo12O40·2H2O的合成、性质和晶体结构

用电解法制备了有机-无机自由基盐(DBTTF)6PMo12O40·2H2O.用红外光谱、电子光谱和电子自旋共振谱进行了表征,测定了其磁化率、导电性和单晶的晶体结构,该晶体属三斜晶系,P1空间群,晶胞参数为a=1.378 7(7)nm,b=1.420 4(2)nm,c=1.570 2(2)nm,α=104.570(8)°,β=103.41(2)°,γ=95.80(2)°,V=2.853(2)nm3,Z=1,Dc=2.142 Mg·m-3,R=0.072 7.     

Hybrid Tungstocuprate [Cu(2,2'-bpy)3]2H4[CuW12O40]·6H2O Based on Keggin Polyoxoanion [CuW12O40]6-with CuⅡas Heteroatom

A novel hybrid tungstocuprate(Ⅱ) [Cu(2,2'-bpy)3]2H4[CuW12O40]·6H2O(2,2'-bpy=2,2'-bipyridine) was synthesized via hydrothermal method and characterized using elemental analyses, IR, UV, XPS, TG-DSC, EPR, and X-ray single crystal diffraction. The structural analysis shows that the complex consists of an unusual Keggin-type polyoxoanion [CuW12O40]6- and a pair of chiral complex cations [Cu(2,2'-bpy)3] together with four protons and six crystallization water molecules, and the Keggin polyoxoanion is connected with [Cu(2,2'-bpy)3] via multiple C-H…O hydrogen bonds resulting in a dimer.     

新型超分子化合物（NH3CH2CH2NH2）3[PW12O40].11H2O晶体的水热合成与表征

首次用水热合成方法报道了超分子化合物（ＮＨ３ＣＨ２ＣＨ２ＮＨ２）３「ＰＷ１２Ｏ４０」．１１Ｈ２Ｏ通过元素分析、ＩＲ光谱、热重分析和Ｘ射线单晶衍射确定了晶体结构,结构分析表明：该晶体属于单斜晶系,Ｐ２１／ｎ空间群,晶胞参数：ａ＝１．８５５９（４）ｎｍ,ｂ＝１．３５１３（３）ｎｍ,ｃ＝２．０４４１（４）ｎｍ,β＝９５．６（３）°,Ｖ＝５．１０３（２）ｎｍ＾３,Ｚ＝４。Ｒ１＝０．０７７５,ｗＲ２＝０．１９５４。     

三维超分子化合物[Ni（DMF）6]2[SiMo12O40]·H2O的合成、晶体结构及表征

合成了一个新的三维超分子化合物[Ni（DMF）6]2[SiMo12O40]·H2O,通过红外光谱、X射线单晶衍射和热重分析等手段对其结构进行了表征．单晶结构解析结果表明,标题化合物属于三方晶系,船空间群,晶胞参数为：a=1．5902（4）nm,b=1．5902（4）nm,c=3．2281（17）nm,V=7．069（4）nm^3,Z=3,Dc=1．994g／cm^3,μ=2．032mm^-1．F（000）：4146,R1=0．0516,ωR2=0．1453．配合物中镍离子采用6配位的八面体配位构型,晶体堆积中通过多种分子间氢键作用形成三维网状结构．     

聚金属氧酸盐[(C4H9)4N]6[PMo12O40]2·0.5H2O的晶体结构

在乙腈-水混合溶剂中培养得到了聚金属氧酸盐[(C4H9)4N]6[PMo12O40]2.0.5H2O的单晶.X射线衍射结构分析表明,该晶体属于单斜晶系,C2/c空间群,晶胞参数:a=4.996(10)nm,b=1.411(3)nm,c=2.633(5)nm,β=114.804(4)°,V=16.844 nm3,Z=1,R1=0.0843,wR2=0.2546.化合物分子由两个多阴离子[PMo12O40]3-,6个四丁基胺阳离子[n-Bu4N]+和0.5个结晶水组成.     

Hydrothermal Synthesis and Crystal Structure of One Rare Earth Substituted Keggin-Type Germanotungstate [Cu(en)2]2[Cu(en)2(H2O)]2H3{[Cu(en)2]2[Na2(H2O)1.75][K(H2O)3][Dy2(H2O)2 (GeW11O39)3]} · 6H2O

A novel germanotungstate derivative based on the dysprosium cation and monovacant Keggin anion, [Cu(en)₂]₂[Cu(en)₂(H₂O)]₂H₃{[Cu(en)₂]₂[Na₂(H₂O)_1.75][K(H₂O)₃][Dy₂(H₂O)₂(GeW₁₁O₃₉)₃]} · 6H₂O(en = ethylenediamine) 1, has been synthesized by hydrothermal method and characterized by elemental analysis, IR-UV spectroscopy, thermal analysis and single-crystal X-ray diffraction. In the compound, one kind of clusters with the Dy³⁺/[GeW₁₁O₃₉]^8? ratio of 2:3 was observed. Especially, the 2:3 type displays the novel cluster based on the rare earth and monolacunary Keggin polyoxometalate.     

Synthesis and photocatalytic properties of a new heteropolyoxoniobate compound: K10[Nb2O2(H2O)2][SiNb12O40)·12H2O

The synthesis and photocatalytic properties of a heteropolyoxoniobate, K(10)[Nb(2)O(2)(H(2)O)(2)][SiNb(12)O(40)]·12H(2)O (1), are reported, revealing an important role of Zr(4+) additives in the crystallization. Compound 1 exhibits overall photocatalytic water splitting activity, and its photocatalytic activity is significantly higher than that of Na(10)[Nb(2)O(2)][SiNb(12)O(40)]·xH(2)O (2). Fluorescence lifetime measurements suggest that the enhanced photocatalytic activity of 1 likely results from a larger yield of longer-lived charge trapping states in 1 due to the coordination of one water molecule to the bridging Nb(5+), leading to highly unsymmetrical seven-coordinated Nb(5+) sites.     

有机-无机杂化化合物[Cu（μ-cbdca）（H2O）]n的电子结构及铁磁性

利用基于密度泛函理论(DVF)的第一性原理的FP_LAPW方法,对以铜离子为磁性中心的化合物[Cu(μ-cbdca)(H2O)]n(cbdca=cyclobutanedicarboxylate)的电子结构及磁性质进行了计算.对该材料的铁磁性、反铁磁性和非磁性三种状态下的总能量进行了计算.计算结果表明,[Cu(μ-cbdca)(H2O)]n的铁磁态能量最低,该化合物为稳定的铁磁性物质,该结果与实验吻合较好.对原子磁矩的计算结果发现,铜原子对化合物磁性的贡献较大,双齿配体上的氧原子和碳原子的贡献相对较小.     

(NH4)15[La(PMo9V2O39)2].6H2O 杂多配合物对苯酚羟化的催化作用

合成了(NH4)15[La(PMo9V2O39)2].6H2O杂多配合物, 并考察其对苯酚过氧化氢羟化反应的催化活性. 探讨了温度、催化剂用量、反应时间、 n(PhOH)/n(H2O2)摩尔比以及反应介质的pH值对反应的影响. 实验结果表明, 以甲醇为溶剂、 n(PhOH)/n(H2O2)=1∶2、反应体系的pH值为5左右、反应温度343 K、反应时间约4 h的条件下, 苯酚转化率可达44.30%, 对苯二酚产率达43.35%. 并采用ICP、 IR、 UV和XRD等技术, 对(NH4)15[La(PMo9V2O39)2].6H2O进行表征, 初步证实了(NH4)15[La(PMo9V2O39)2].6H2O具有Keggin结构.     

An organic-inorganic hybrid polyoxometalate based on the dodecatungstate building block: [Ni(phen)(H2O)3]2[Ni(H2O)5][H2W12O40] · 6H2O

An organic-inorganic hybrid polyoxometalate [Ni(phen)(H₂O)₃]₂[Ni(H₂O)₅][H₂W₁₂O₄₀]?·?6H₂O (phen?=?1,10-phenanthroline) has been isolated and characterized by IR, UV, electrochemistry and single-crystal X-ray diffraction. X-ray crystallographic study indicates that the title compound is monoclinic, space group C2/c, with lattice constants a?=?21.7672(17), b?=?16.1189(12), c?=?20.7949(16)?Å, β?=?107.8440(10)°, V?=?6945.2(9)?ų, D _c?=?3.528?Mg?m^?3, F(000)?=?6600, Z?=?4, R ₁?=?0.0372, wR ₂?=?0.0845. The molecular fragment of the title compound consists of two supporting [Ni(phen)(H₂O)₃]²⁺ coordination cations, one supporting [Ni(H₂O)₅]²⁺ unit, one metatungstate polyoxoanion [H₂W₁₂O₄₀]^6? and six H₂O molecules of crystallization.     

三维超分子化合物[Ag2(tdpc)(bipy)2][ Ag2(bipy)2(H2O)]·12H2O的合成和晶体结构

以银离子、3,3 ',4,4'-二苯硫酮四羧酸阴离子(tdpc)和4,4'-联吡啶(bipy),合成了一种新型化合物[十二水合(3,3',4,4'-二苯硫酮四羧酸)(4,4'-联吡啶)水合银][ Ag2 (tdpc)(bipy)2][ Ag2 (bipy)2 (H2O)]·12H2O,该化合物为链状结构,Ag…Ag相互...     

Hybrid Tungstocuprate [ Cu（2,2＇-bpy）3]2 H4 [ CuW12O40 ]· 6H2O Based on Keggin Polyoxoanion [CuW12O40]^6- with Cu^Ⅱ as Heteroatom

A novel hybrid tungstocuprate （ Ⅱ ） [ Cu （2,2＇-bpy） 3 ] 2 H4 [ CuW12O40 ] · 6H2O （ 2,2＇-bpy = 2,2＇-bipyfidine） was synthesized via hydrothermal method and characterized using elemental analyses, IR, UV, XPS, TG-DSC, EPR, and X-ray single crystal diffraction. The structural analysis shows that the complex consists of an unusual Keggin-type polyoxoanion [ CuW12O40 ]^6- and a pair of chiral complex cations [ Cu（2,2＇-bpy） 3 ]^＋ together with four protons and six crystallization water molecules, and the Keggin polyoxoanion is connected with [ Cu （2,2＇-bpy）3 ]^＋v/a multiple C-H…O hydrogen bonds resulting in a dimer.