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)].     

[Co（bim）x]配合物修饰的｛P2Mo5O23｝超分子的合成、晶体结构和电化学性质

利用水热技术合成了一种新型[Co(bim)x]配合物修饰的磷钼多金属氧酸盐超分子化合物[Co(bim)3] [Co(Hbim)2( H2 O) P2 Mo5 O23]·5H2O.通过元素分析、红外光谱、热重分析和X射线单晶衍射对化合物进行了表征.化合物属于单斜晶系,P2(1)空间群;晶胞参数:a=11.505 (2) nm,b=19.123 (3) nm,c=13.852(2) nm,α=90.00°,β=100.073(2)°,γ=90.00°,V=3 000.6(8)nm3,F(000)=1 756.0,Z=2.并测试了合成化合物的电化学性质.     

[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.     

[Ln2（HINC）4]6+（Ln=Ce,Eu）二聚体修饰的两个Dawson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2个新的双核稀土-异烟酸配合物修饰的Dawson型有机-无机杂化化合物[Ln2(HINC)4(H2O)8(P2W18O62)]·nH2O(Ln=Ce(1),Eu(2);n=16(1),9(2);INC=4-吡啶羧酸/异烟酸).化合物1与2同构,并通过红外光谱、元素分析和X-射线单晶衍射方法确定了该化合物的晶体结构.单晶结构分析表明化合物1属于三斜晶系,P-1空间群,晶胞参数a=1.323 6(3)nm,b=1.865 0(4)nm,c=2.287 2(5)nm,α=67.26(3)°,β=78.01(3)°,γ=70.34(3)°,V=4.883 8(17)nm3,Z=2.化合物2也属于三斜晶系,P-1空间群,晶胞参数a=1.320 1(2)nm,b=1.856 9(3)nm,c=2.285 6(4)nm,α=67.378(2)°,β=77.745(3)°,γ=70.039(3)°,V=4.839 8(13)nm3,Z=2.     

一个新颖镍配位阳离子修饰的还原型钼磷酸盐：Ni[Mo6O12(OH)3(PO4)(HPO4)3]2][Ni(H2O)2][Ni(H2O)(bipy)2]4·5H2O

水热合成并通过红外、热重、单晶X-射线衍射表征了一个新颖镍配位阳离子修饰的还原型钼磷酸盐,Ni[Mo₆O₁₂(OH)₃(PO₄)(HPO₄)₃]₂][Ni(H₂O)₂][Ni(H₂O)(bipy)₂]₄·5H₂O。单晶X-射线衍射研究表明,两个{Mo₆P₄}簇单元通过一个镍离子连接形成一个Ni[Mo₆P₄]₂二聚结构单元,其进一步和其他的镍配位阳离子连接成钼磷酸盐一维链状结构。在H₂O₂存在下的液－固体系中,使用该化合物催化氧化苯甲醛的探针反应结果表明,该化合物具有较高的催化氧化活性。     

含一价铜配合物的新型双金属钼氧簇合物[5-(4-Br-Ph)-2,4'-Hbpy]2·[CuⅠ(5-(4-Br-Ph)-2,4'-bpy)2]2[Mo8O26]的水热合成及晶体结构

采用水热法合成出一种含一价铜配合物的新型双金属钼氧簇合物[5-(4-Br-Ph)-2,4'-Hbpy]2[Cu(5-(4-Br-Ph)-2,4'-bpy)2]2[Mo8O26],并通过X射线单晶结构分析、红外光谱分析、元素分析以及X射线粉末衍射分析对该化合物的结构进行了表征.结果表明,该化合物属单斜晶系,P21/c空间群,晶胞参数a=1.4411(3)nm,b=1.3924(3)nm,c=2.5183(5)nm,β=99.06(3)°,V=4.990(17)nm3,Z=2;该化合物是由一价铜配合物{Cu(5-(4-Br-Ph)-2,4'-bpy)2}+与{β-Mo8O26}4-簇通过共价配位键连接形成的新型多金属钼酸盐,其中游离的质子化配体作为抗衡阳离子.     

Na6In4[P7O24(OH)5]·4H2O的水热合成与表征

具有开放骨架结构的金属酸盐在作为微孔材料、非线性光学材料、催化剂载体和离子交换剂等方面具有应用前景 [1] .自从报道第一个具有微孔结构的磷酸铝 [2 ]以来 ,许多其它具有开放骨架结构的金属磷酸盐被合成出来 ,它们的性质和潜在的应用研究也备受关注 [3～ 8] .本文采用温和条件下的水热法 ,合成得到了具有螺旋链状结构的磷酸铟钠盐 [Na6 In4 [P7O2 4 ( OH) 5]· 4H2 O,并采用 X射线单晶衍射方法进行结构测定 ,其结构中包含了共顶角的多面体连接成的螺旋链 ,链间的连接形成多面体四元环和八元环 ,3个四元环围成了一个三配位氧为中心…     

以稀土为连接单元基于Anderson型[Al(OH)6Mo6O18]3-的一维拓展结构的合成及性质研究

在常规条件下合成4个新型的稀土-Anderson型多金属氧酸盐拓展结构化合物(C5H9NO2)2[Ln(H2O)7AlMo6H6O24].11H2O(Ln=La(1),Ce(2),Pr(3),Gd(4);C5H9NO2=脯氨酸),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化合物晶体结构进行了表征。结构分析表明:以上4个化合物是同构的,均结晶在单斜C2/c空间群。在这些结构中,[Al(OH)6Mo6O18]3-首先通过稀土离子连接形成一维链,相邻的链再进一步通过脯氨酸和结晶水分子的氢键作用形成三维超分子结构化合物。我们以化合物1为代表研究了这类化合物的光催化性能,在紫外光照射下表现出很好的降解RhB(罗丹明B)的光催化性质。     

[Ni(en)3]4[HVⅣ12VⅤ6O42(PO4)]复合物的合成及晶体结构

A new complex [Ni(en)₃]₄[HV^Ⅳ₁₂V^Ⅴ₆O₄₂(PO₄)] has been hydrothermally synthesized and characterized by X-Ray diffraction, IR and Elemental analysis. Single crystal X-ray analysis indicates that this compoud crystallizes in cubic system,space group Im 3m with a=17.4081(2)?, V=5275.38(10)?³, R=0.0420, wR=0.1055, Z=2, D_c=1.663g·cm^-3, μ=2.297mm^-1, F(000)=2636. The crystal structure consists of [Ni(en)₃]²⁺ cations and {HV₁₈O₄₂(PO₄)}^8- cluster anion which construct from 18 {VO₅} square pyramids. The VO₅ pyramids joined each other to form a {V₁₈O₄₂} cage hosting a tetrahedral {PO₄}^3- moiety with disordered oxygen atoms. CCDC: 185574.     

[M(2,2'–bpy)2]2SiW12O40（M=Mn,Co;bpy=联吡啶）的合成、结构及其电催化水产氧性能

用水热法合成了过渡金属联吡啶配阳离子硅钨杂多酸:[M(2,2’-bpy)2]2SiW12O40(M=Mn(1)和M=Co(2)),采用红外光谱、元素分析、热重和单晶X射线衍射对其进行了表征。结果表明,化合物1和2是异质同构体,具有二维格子框架结构。初步研究了2种化合物的电催化H2O析出O2性能,发现化合物1对电催化H2O析出O2有一定的催化作用。     

[Zn(H2PO4)4] clusters and ∞[Zn2(HPO4)3(H2PO4)2] layers in two new zinc phosphates templated by [H2(4-amino-2.2.6.6-tetramethylpiperidine)] cations

Two zinc phosphates (ZnPO), [H₂(N₂C₉H₂₀)]·[Zn(H₂PO₄)₄] (I) and [H₂(N₂C₉H₂₀)]₂·[Zn₂(HPO₄)₃(H₂PO₄)₂]·H₂O (II), are synthesized under hydrothermal conditions using 4-amino-2.2.6.6-tetramethylpiperidine as organic template. I crystallizes in space group with , , , α=92.57(1)°, β=89.76(1)°, γ=102.16(2)°, and Z=2. Its structure, refined to R=0.029 and R_w=0.076 for 4279 independent reflections, consists of [Zn(H₂PO₄)₄]²⁻ clusters held together through strong hydrogen bonds to form pseudo-layers between which the doubly protonated amine molecules are inserted. II is monoclinic, C2, with , , , β=103.72(5)°, and Z=4 (R=0.079, R_w=0.268, 2477 independent reflections). The structure of II consists of _∞[Zn₂(HPO₄)₃(H₂PO₄)₂]⁴⁻ inorganic (2D) layers built up from vertex-sharing [ZnO₄] and [(H₂/H)PO₄] tetrahedra. Organic cations and water molecules ensure the connection between these layers via hydrogen bonds. It is shown that numerous (1D), (2D), e.g., [H₂(N₂C₉H₂₀)]₂·[Zn₂(HPO₄)₃(H₂PO₄)₂]·H₂O, and (3D) (ZnPO) result from the condensation of the [Zn(H₂PO₄)₄]²⁻ clusters.     

Supramolecular stabilization of the phosphite-based polyoxomolybdate [Mo6(PO3)(HPO3)3O18]

A novel phosphite-based hetero-polyoxomolybdate, [Mo₆(PO₃)(HPO₃)₃O₁₈]⁹⁻, has been isolated and structurally characterized. The most striking feature of this polyanion is the presence of peripheral phosphite groups linked to the MoO₆ octahedra. In the solid state, this cluster shows strong hydrogen bonding interactions that apparently play a key role in its stabilization and isolation from solution.     

Synthesis and x-ray crystal structure of [PPN]+2[RuIr4(CO)9(μ2-CO)6]2-

The dianion [RuIr₄(CO)₁₅]^2- has been obtained by reductive carbonylation of mixtures of Ir₄(CO)₁₂ and RuCl₃ · χ H²O, and the bis(triphenylphosphine)-iminium salt has been characterized by single-crystal X-ray diffraction techniques. Crystal data: [((C₆H₅)₃P)₂N]₂[RuIr₄(CO)₁₅], space group P$\text{1}$ (Z  2), a  11.425(3), b  14.141(2), c  25.979(5) Å, α  84.55(1), β  83.53(2), γ  80.71(2)°. The mixed-metal cluster has a structure with an elongated trigonal bipyramidal array of metal atoms in which Ru occupies an apical position. The anion is unstable in vacuum or in an N₂ atmosphere yielding predominantly another mixed-metal species which is not as yet fully characterized. Upon reexposure to CO, this latter species is converted back to [RuIr₄(CO)₁₅]^2-, plus additional products.     

[Pt2(P2O4H2)4]4-和[Pt2(P2O4CH4)4]4-基态和激发态性质的理论研究

采用从头计算MP2和CIS方法分别优化等电子双核d⁸配合物[Pt₂(P₂O₄H₂)₄]^4-和[Pt₂(P₂O₄CH₄)₄]^4-的基态和激发态结构。结果表明基态Pt-Pt距离分别为0.290 5和0.298 7 nm，与实验的0.292 5和0.298 0 nm符合。NBO计算的Pt-Pt键级以及Pt原子间伸缩振动说明Pt-Pt相互作用具有吸引本质。CIS计算揭示电子激发到Pt-Pt的σ(p_z)成键轨道使得相互作用增强。保持激发态几何，含时密度泛函理论(TD-DFT)计算的溶液发射分别为449和475 nm，与实验值512和510 nm接近。     

新型微孔磷酸铝[C4N2H14]2+[H2Al3P3O14]2-的合成、结构及相转变

以3-甲氨基丙胺为结构导向剂,在水热条件下合成了1个具有三维开放骨架结构的微孔磷酸铝化合物[C4N2H14][H2Al3P3O14](1),并通过X射线单晶衍射确定了其结构,用粉末X射线衍射(PXRD)、热重(TG)、元素分析(ICP及CHN)和扫描电子显微镜(SEM)对其进行表征.结果表明,化合物1属正交晶系,Pbca空间群,晶胞参数a=1.59839(11)nm,b=0.99402(6)nm,c=1.82261(11)nm,V=2.8958(3)nm3.化合物1的无机骨架由铝氧多面体(AlO5/AlO6)和磷氧四面体(PO4)严格交替连接构筑而成,形成了在[010]方向上具有一维十元环孔道的三维阴离子开放骨架.每个P原子通过桥氧原子与相邻的4个Al原子相连,而Al原子除了通过桥氧原子与相邻的4个P原子相连之外,还通过羟基的桥氧原子与1个或2个Al原子相连,分别形成五配位和六配位的Al.化合物1在550℃空气或氧气气氛下灼烧5 h后转变为具有ATV分子筛结构的微孔磷酸铝分子筛AlPO4-25,且一直稳定到800℃.     

Two mixed valent molybdenophosphates with a tunnel structure closely related to K0.17MoP2O7: Pb2(PbO)2Mo8(P2O7)8 and PbK2Mo8(P2O7)8

Two new mixed valent Mo(III)/Mo(IV) diphosphates containing lead Pb₂(PbO)₂Mo₈(P₂O₇)₈ and PbK₂Mo₈(P₂O₇)₈ have been synthesized. The [Mo₈P₁₆O₅₆]∞ frameworks of these phosphates are closely related to that of K_0.17MoP₂O₇: the MoO₆ octahedra and P₂O₇ groups form two sorts of large eight-sided tunnels. They are occupied in an ordered way by PbO chains and Pb²⁺ cations in Pb₂(PbO)₂Mo₈(P₂O₇)₈ and by K⁺ and Pb²⁺ cations in PbK₂Mo₈(P₂O₇)₈. It results in different symmetries of these two structures, which are tetragonal and monoclinic, respectively, showing the great flexibility of these mixed frameworks, susceptible to accommodate various species with different sizes.     

[Hg5O2(OH)4][(UO2)2(AsO4)2]: A complex mercury(II) uranyl arsenate

Under mild hydrothermal conditions UO₂(NO₃)₂·6H₂O, Hg₂(NO₃)₂·2H₂O, and Na₂HAsO₄·7H₂O react to form [Hg₅O₂(OH)₄][(UO₂)₂(AsO₄)₂] (HgUAs-1). Single crystal X-ray diffraction experiments reveal that HgUAs-1 possesses a pseudo-layered structure consisting of two types of layers: and . The layers are complex, and contain three crystallographically unique Hg centers. The coordination environments and bond-valence sum calculations indicate that the Hg centers are divalent. The layers belong to the Johannite topological family. The and layers are linked to each other through μ₂-O bridges that include Hg?O=U=O interactions.     

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.     

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     

Supramolecular structures containing ‘isolated’ pentaborate anions and non-metal cations: Crystal structures of [Me3NCH2CH2OH][B5O6(OH)4] and [4-MepyH, 4-Mepy][B5O6(OH)4]

The solid-state structures of two non-metal pentaborates [Me₃NCH₂CH₂OH][B₅O₆(OH)₄] (1) and [4-MepyH, 4-Mepy][B₅O₆(OH)₄] (2) have been determined by single-crystal X-ray diffraction methods. Structures 1 and 2 both contain supramolecular pentaborate frameworks held together by extensive H-bond interactions. The framework of 1 exists essentially as planes of pentaborate anions linked via three pairwise ‘planar’ β → α interactions, with a fourth β → β interaction crosslinking the planes. The framework of 2 is very similar except that one of the three pairwise linkages within the plane is replaced by pairwise ‘step-like’ bifurcated H-bonds to both α sites of a neighboring anion. The cations in 1 and the cations and neutral 4-Mepy ligands in 2 are present in the framework cavities and channels, with additional H-bond interactions existing between cations and anions.