三维超分子化合物[H2bbi]3[α-PMo12O40]2的水热合成与晶体结构

利用水热技术合成了一个以Keggin型多金属氧酸盐和柔性有机配体为建筑块的三维超分子化合物[H2bbi]3[α-PMo12O40]2(1)(bbi=1,4-双-(咪唑-1-基)丁烷),用X-射线单晶衍射、元素分析、红外光谱和X-射线粉末衍射对晶体结构进行了表征.X-射线单晶衍射显示,该晶体属于三斜晶系,P-1空间群,a=1.183 60(9)nm,b=1.209 32(10)nm,c=1.77728(15)nm,α=74.089 0(10)°,β=70.949 0(10)°,γ=71.816 0(10)°,V=2.242 1(3)nm3,Z=2,Dc=3.109g/cm3,F(000)=2 300,μ=3.39mm-1,S=1.047,R1=0.035 0,wR2=0.077 6[I>2σ(I)].     

以还原型钼磷酸盐[P4MoV6O28(OH)3]9-为建筑单元构筑新型多维延展结构材料

向MoO₃, H₃PO₄和bpy(4,4′-bipyridine)组成的反应体系中分别引入Cd(OAc)₂·2H₂O 和MnCl₂·4H₂O, 在水热条件下合成了两种基于还原型钼磷酸盐[P₄Mo₆O₂₈(OH)₃]^9-(简称{P₄Mo₆})为建筑单元构筑的新型多维延展型无机-有机杂化材料(H₂bpy)₂[Cd(H₂O)]₃[Cd(HPO₄)₆(PO₄)₂(OH)₆(MoO₂)₁₂]·5H₂O(1)和 (H₂bpy)₃[Mn(H₂O)₂]₂ [Mn(HPO₄)₆(PO₄)₂(OH)₆(MoO₂)₁₂]·10H₂O(2), 并通过元素分析、红外光谱、热重分析和X射线单晶衍射对其进行了表征。结果表明, 化合物1和2均属于三斜晶系, P1 空间群。化合物1的阴离子[Cd(H₂O)]₃[Cd(HPO₄)₆(PO₄)₂(OH)₆(MoO₂)₁₂]^2-是由二聚体 Cd[P₄Mo₆]₂通过{Cd₃}簇依次连接形成的一维无机链状结构; 化合物2的阴离子[Mn(H₂O)₂]₂[Mn(HPO₄)₆(PO₄)₂(OH)₆(MoO₂)₁₂]^3-则是由二聚体Mn[P₄Mo₆]₂通过Mn²⁺离子连接形成的二维无机层状结构。这2种无机延展结构均同质子化的bpy通过氢键作用形成不同的三维超分子网络。同时还探讨了化合物2的电化学性质。     

有机-无机复合磷钨酸盐[HTA]3[α-PW12O40]·6H2O的合成与晶体结构（英文）

利用CuCl2·2H2O,1,2,4-三氮唑(TA),L-丝氨酸与Na3[α-PW12O40]·6H2O在乙醇的水溶液中合成了一种有机-无机复合Keggin结构磷钨酸盐[HTA]3[α-PW12O40]·6H2O;利用红外光谱和X射线单晶衍射表征了合成产物的结构,利用元素分析测定了其组成.结果表明,标题化合物属于菱方晶系R-3空间群,晶胞参数为:a=1.793 73(12)nm,b=1.793 73(12)nm,c=2.440 7(3)nm,α=β=90°,γ=120°,Z=6,V=6.800 7(11)nm3,Dc=4.682g·cm-3,GOOF=1.079,R1=0.051 6,wR2=0.137 4.就分子结构而言,标题化合物分子由一个饱和Keggin结构多阴离子[α-PW12O40]3-,三个游离的质子化[HTA]+阳离子和六个结晶水分子组成.     

氨基酸功能化多钼酸盐[(Gly)_2(H_2O)_2Cu]K_3[Al(OH)_6Mo_6O_(18)]·7H_2O的合成及表征

在常规条件下合成了一种新型的氨基酸功能化的多金属氧酸盐化合物[(Gly)2(H2O)2Cu]K3[Al(OH)6Mo6O18]·7H2O,并通过元素分析、红外光谱、紫外可见光谱、热重分析和X射线单晶衍射等方法对其晶体结构进行了表征.结构分析表明:该晶体属于三斜晶系,Pi空间群,晶胞参数α=0.810 53(16)am,6=1.139 4(2) nm,c=1.824 7(4)nm,α=93.96(3)°,β=92.89(3)°,γ=108.90(3)°,V=1.585 8(5)nm3,Z=2.     

以[α-P2W18O62]6-阴离子为构筑块的一维链状稀土配位聚合物[Nd(DMF)6(H2O)2][Nd(DMF)6(H2O)]P2W18O62的合成﹑结构及性质研究

以Nd2O3,DMF和α-H6P2W18O62·nH2O等为原料合成了Dawson结构杂多阴离子有机-无机配位聚合物[Nd(DMF)6(H2O)2][Nd(DMF)6(H2O)]P2W18O62,并对其进行了IR,UV光谱表征及电化学性质研究.X-射线衍射单晶结构分析结果表明,晶体属单斜晶系,Cc空间群,晶胞参数a1.8991(3)nm,b=2.2047(3)nm,c=2.6448(4)nm,β=102.272(3)°,并有Z=4,R1=0.043 8,wR2=0.1107.聚合物中存在2种构型的Nd配离子,Nd(1)以九配位的三加冠三棱柱结构通过端氧与[P2W18O62]6-阴离子赤道位的W相连,Nd(2)以九配位畸变的单加冠四方反棱柱结构通过端氧与[P2W18O62]6-阴离子极位的W相连,从而构成分子结构单元[{Nd(DMF)6(H2O)2}{Nd(DMF)6(H2O)}(P2W18O62)],毗邻的结构单元又通过W-O-Nd(1)-O-W桥联形成一维锯齿无限链状结构.     

[Cu（Dfo）3]2+修饰的Keggin型超分子化合物的合成与晶体结构

利用水热合成方法合成了1个新的Keggin基有机-无机杂化化合物[Cu2(Dfo)6(SiMo12O40)],并通过元素分析、红外光谱和X射线单晶衍射方法确定了该化合物的晶体结构.结构分析表明该化合物属于立方晶系,Pa-3空间群,晶胞参数a=b=c=2.081 82(3)nm,α=β=γ=90°,V=9.022 6(4)nm3,Z=4,R1=0.064 9,ωR2=0.156 1.将目标化合物制成碳糊电极,利用循环伏安法研究了其电化学行为及其对NO2-还原的电催化性能.     

[4,4′-bpyH2][4,4′-bpyH] [Cr(OH)6(Mo6O18)]和[4,4′-bpyH]3 [Al(OH)6(Mo6O18)]·2H2O的合成及晶体结构

通过水热方法合成了两种新的B-Anderson型多钼氧酸盐[4 ,4′-bpyH2][4 ,4′-bpy H][Cr( OH)6( Mo6O18)](1)和[4 ,4′-bpyH]3[Al(OH)6( Mo6O18)].2 H2O(2) ,通过元素分析、IR光谱和单晶X射线衍射对其进行了表征.化合物1和2都是分离结构.化合物1分子由2个晶体学独立1/2 B-Anderson类型[Cr(OH)6( Mo6O18)]3 -多阴离子,1个双质子化的[4 ,4′-bpyH2]2 +阳离子和1个单质子化的[4 ,4′-bpyH]+阳离子组成,化合物2则是由1个晶体学独立完整的B-Anderson型[ Al( OH)6( Mo6O18)]3 -多阴离子, 3个单质子化的[4 ,4′-bpyH]+阳离子和2个晶格水分子组成.借助4 ,4′-bpy分子间的π-π堆积作用,化合物1和2形成三维超分子结构.     

K3H3[As2W21O69（H2O）]·19H2O的合成及晶体结构（英文）

利用二缺位K14[As2W19O67]·nH2O前驱体在酸性条件下的结构转变得到了饱和的砷钨酸盐K3H3[As2W21O69(H2O)]·19H2O(1),借助傅立叶变换红外光谱和X射线单晶衍射对其结构进行了表征.结果表明,化合物1的多阴离子骨架由两个相同的三缺位[α-AsW9O33]9-片段通过三个W=O基团连接而成.值得提及的是,在化合物1的阴离子骨架中心空腔中存在一个游离的水分子.     

超分子化合物（C6H8N）6(PW12O40)（OH）3·5H2O的结构、电化学性质和热稳定性

通过水热合成方法合成了三维超分子化合物(C6H8N)6(PW12O40)(OH)3.5H2O,采用IR、单晶X射线衍射法、TG/DTG及循环伏安法对标题化合物进行结构、热稳定性和电化学性质研究.结构解析表明,化合物属于六方晶系,P-3空间群,晶胞参数a=1.393 01(14)nm,b=1.393 01(14)nm,c=1.025 70(10)nm,V=1.723 7(3)nm3,Z=1,Dc=3.452g/cm3,最终偏差因子R1=0.068 3,wR2=0.166 7.该化合物通过氢键作用形成3D超分子结构.     

Anderson-B-型多金属氧酸盐[Co(2,2''-bipy)3]H-[Al(OH)6(Mo6O18)]·5H2O的合成及晶体结构

以AlCl3·6H2O、Na2MoO4·2H2O、CoCl2·6H2O和2,2'-联吡啶为主要原料合成了Anderson-B-型多金属氧酸盐[Co(2,2'-bipy)3]H[Al(OH)6(Mo6O18)]·5H2O,进行了红外光谱、紫外光谱、差热分析和单晶结构测定.晶体学测定结果表明,化合物属于三斜晶系,Pi空间群,晶胞参数:a=1.216 0(2),b=1.221 5(2),c=1.780 0(4)nm,α=86.83(3)°,β=88.76(3)°,γ=89.82(3)°,V=2.639 4(9)nm3,Z=2,R1=0.079 4,wR2=0.176 6.化合物结构分析表明,在晶体学上,标题化合物分子是由1个[Co(2,2'-bipy)3]2+配阳离子,1个H+离子,2个1/2[Al(OH)6(Mo6O18)]3-多阴离子和5个结晶水分子组成.多阴离子[Al(OH)6(Mo6-O18)]3-借助水分子和金属配离子通过超分子作用形成二维网状结构,网状结构之间又借助超分子作用形成三维无限伸展结构.差热分析表明,标题化合物的失重过程分为2步,多阴离子骨架破坏温度为547.5℃.     

含新颖一维金属氧簇阳离子的聚金属氧簇化合物[{M(2,2'-bipy)}5O14]4- [2,2'-H2bipy]2(As2W18O62)2•8H2O (M＝Mo, W)的合成、晶体结构与表征

以Na₂WO₄•2H₂O, Na₂MoO₄•2H₂O, Na₂HAsO₄•7H₂O和2,2'-bipyridine为原料, 在水热条件下制得了含一维阳离子的聚金属氧簇化合物: [{M(2,2'-bipy)}₅O₁₄]₄[2,2'-H₂bipy]₂(As₂W₁₈O₆₂)₂•8H₂O (M＝Mo/W; 2,2'-bipy＝2,2'-bipyridyl), 并用元素分析, IR, TG和单晶X-ray衍射等手段进行了表征. 标题化合物属于单斜晶系, C2/c空间群, a＝4.1721(5) nm, b＝2.4629(5) nm, c＝1.7541(5) nm, β＝91.119(3)°, V＝18.021(5) nm³, Z＝2, R₁＝0.0629, wR₂＝0.1605 [I＞2σ(I)]. 标题化合物的阳离子链由五元金属氧簇构筑块[{M(2,2'-bipy)}₅O₁₄]^2＋通过氧原子桥联而成, 构筑块[{M(2,2'-bipy)}₅O₁₄]^2＋中的五个金属原子呈畸变的“A”字型排布, 阳离子展现出新颖的一维锯齿链状结构.     

Synthesis, crystal structure and properties of a new organic-inorganic hybrid Dawson-like polyoxotungstate [Co(2,2''''-bpy)3]2[Co(2,2''''-bpy)2Cl][Co(2,2''''-bpy)2]H2-[SbW18O60]·4H2O

A new organic-inorganic hybrid polyoxometalate based on Dawson-like polyoxotungstate anion [SbW18O60]9-, formulated [Co(2,2'-bpy)3]2[Co(2,2'-bpy)2Cl][Co(2,2'-bpy)2]H2[SbW18O60]·4H2O (2,2'-bpy= 2,2(-bipyridine) has been synthesized from Sb2O3, Na2WO4, CoCl2, and 2,2'-bipyridine materials by hydrothermal method, and which was characterized by elemental analyses, IR, XPS, EPR, TG, and X-ray single crystal diffraction. Structure analysis shows that the polyoxoanion self-assembled under hydrothermal conditions consists of a Dawson-like polyoxotungstate cluster anion [SbW18O60]9- encapsulating a pyramidal {SbO3} group within the {W18} cluster cage. EPR spectra show that the high-spin octahedral CoⅡ and low-spin CoⅡ ions coexist in the title compound. Magnetic properties indicate that the compound is antiferromagnetic.     

具有[344484]笼状结构单元的微孔磷酸镓Ga3P2O8(OH)3(H2O)的合成、晶体结构及表征

Open-framework metal phosphates have been the subject of intense research owing to their interesting structural chemistry and potential applications in catalysis and ion exchange. The gallium phosphate family has exhibits rich structural chemistry. A novel gallium phosphate Ga₃P₂O₈(OH)₃(H₂O)(GaPO-CJ36) has been prepared in a hydrothermal reaction system of GaO(OH)-H₃PO₄-Co(chxn)₃Cl₃-H₂O at 180 ℃ for 7 days. Single-crystal X-ray analysis shows that GaPO-CJ36 crystallizes in the P2₁/c space group with a=1.833 35(12) nm, b=0.503 94(3) nm, c=1.062 90(9) nm, V=0.982 01(12) nm³, and Z=4. The connection of GaO₂(OH)₃(H₂O) octahedra, PO₄ and GaO₄ tetrahedra through vertex oxygen atoms forms a three-dimensional open framework, which contains 8-ring channels along the [010] direction. Its structure is composed of interesting [3⁴4⁴8⁴] cages, which have not been found in known gallium phosphates. CSD: 416779.     

二维层状结构十钒酸盐[K(H2O)2Ni(H2O)6]2[V10O28]的合成及性质(英)

A novel heteropoly compound, containing two kinds of coordinated cations, [K(H₂O)₂Ni(H₂O)₆]₂[V₁₀O₂₈], has been synthesized through routine process and characterized by elemental analyses, IR, ⁵¹V NMR and single crystal X-ray diffraction. It crystallizes in the triclinic system, space group P1 with a=0.87382(17) nm, b=1.075 4(2) nm, c=1.111 1(2) nm, α=65.10(3)°, β=75.01(3)°, γ=70.63(3)°, V=0.884 8(3) nm³ and Z=1. The X-ray analysis reveals that the two kinds of coordinated cations are linked by three shared coordinated water molecules, and K⁺ cations coordinate with ten oxygen atoms: five of which come from V₁₀O₂₈^6- anion, the other five from water molecules. The title compound exhibits extended 2D array building up of V₁₀O₂₈^6- groups connected by ten-coordinated K⁺ cations. The hexahydrated nickel cations Ni(H₂O)₆²⁺ lie in neat apposition to three adjacent V₁₀O₂₈^6- clusters. CSD: 413271.     

[Na(DB18C6)(CH3CN)]2Mo6O19的合成、晶体结构及谱学表征

A novel super-molecular complex, [Na(DB18C6)(CH₃CN)]₂Mo₆O₁₉, was obtained by solvothermal reaction and characterized by elementary analysis, IR, ¹H NMR, gumbc spectrum and X-Ray diffraction experiment. The compound crystallizes in monoclinic space group P2₁/n with a=1.187 1(3) nm, b=2.096 3(6) nm, c=1.415 8(4) nm, β=110.854(5)° and Z=4. The complex contains four basic units: Na⁺, CH₃CN, DB₁₈C₆和Mo₆O₁₉^2-. Sodium ions located in the cavity of dibenzo-18-crown-6 with 6 Na-O bonds and the crown ether-sodium ion complex is supported on the terminal oxygen atoms of the typical Lindqvist isopolyanion Mo₆O₁₉^2- via the coordinative interactions. Mo₆O₁₉^2- located between two DB₁₈C₆ and led to the formation of the “hamburger” structure. The crystal is stabilized by van der waals force and interaction of π-π system. CCDC: 272936.     

一种含[Ni(CN)4]2-和[Cu(pn)]2+构筑元组成的超分子配合物的合成、单晶结构和磁学性质

A cyano-bridged heterometallic supramolecular complex {[Cu(pn)]₃[Ni(CN)₄]₃}_n (1) has been synthesized and structurally characterized by single crystal X-ray diffraction. 1 displays an interesting 3D structure formed by μ₄, μ₃-[Ni(CN)₄]^2- tectons bridging five-coordinated and six-coordinated Cu(II) ions. The magnetic property shows that 1 behaves as weakly ferromagnetic interactions between the adjacent Cu(II) ions through the diamagnetic spacer NC-Ni-CN. CCDC: 624387.     

Synthesis and Crystal Structure of Cucurbit[6]uril Adduct of Hydrogen-bonded Cluster Complex [Mo3(μ3-Se)(μ2-O)3(H2O)6Cl3]+

Reaction of [MoOCl₅]²⁻ with in situ generated H₂Se under hydrothermal conditions (4M HCl, 140 °C) leads to reduction of Mo(V) to Mo(IV) with the formation of a triangular cluster Mo₃(μ₃-Se)(μ-O)₃⁴⁺ in high yield. It is present in HCl solutions as aqua chlorocomplex [Mo₃(μ₃-Se)(μ-O)₃(H₂O)₆Cl₃]⁺ which was isolated and structurally characterized as supramolecular adduct with cucurbit[6]uril (CB[6]), {[Mo₃(μ₃-Se)(μ-O)₃(H₂O)₆Cl₃]₂CB[6]}Cl₂·15H₂O. Dedicated to Professor Dieter Fenske on the Occasion of his 65th Birthday     

[COH(NH2)2]2[Cu(pic)2(ClO4)2]的合成与晶体结构

The title compound was synthesized by reaction of Cu(ClO₄)₂， picolinic acid and carbamide in C₂H₅OH/CH₃CN solution， and characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system， space group Pbca with a=14.0481(8)， b=9.0130(5)， c=18.626(1)?， V=2358.3(2)?³， Z=4， D_x=1.771g·cm^-3， μ=1.235mm^-1 and F(000)=1276. The final R factor is 0.0440 for 1434 observed reflections. The X-ray analysis revealed that the copper(Ⅱ) atom is coordinated by two picolinic ligands in the equatorial plane， while the two oxygen atoms of perchlorate occupy the axial positions of octahedron with lengthened Cu-O distances， resulting in a 4+2 elongated octahedral environment. In the compound， there also exist two protonated carbamide cations for charge balance. CCDC： 195354.     

含季鏻阳离子的[Mo6O19]2-多酸化合物的合成、结构及光催化性能研究

通过使用季鏻盐与钼酸铵在常温条件下合成了含季鏻阳离子的(n-PentylPh₃P)₂[Mo₆O₁₉]多酸化合物,并通过X-射线单晶衍射、红外光谱、紫外光谱、热重分析和电化学对其进行了表征。产物中的季鏻配体上的氢原子通过与多酸阴离子端基氧原子形成氢键而构筑了一维链状结构,并且季鏻配体上的苯环与相邻季鏻配体上的苯环通过π-π作用形成三维层状结构。此外,对该多酸化合物的光催化降解亚甲基蓝的性能进行了研究。