基于[As_2W_(19)O_(67)(H_2O)]~(14-)构筑的含镧砷钨酸盐的合成和结构表征

通过水热法合成了一例[As_2W_(19)O_(67)(H_2O)]~(14-)({As_2W_(19)})构型保持的稀土衍生物K_(14)H_8[La(H_2O)_3As_2W_(19)O_(67)(H_2O)]_2·53H_2O(1),并测定了其晶体结构.同时,通过红外光谱、粉末衍射(XRPD)以及热分析对其进行了表征.X射线单晶结构分析表明,化合物1属于三斜晶系,P-1空间群,晶胞参数为a=1.239 5(10)nm,b=1.847 8(16)nm,c=2.268 5(19)nm,α=68.366(12)°,β=78.215(13)°,γ=78.406(12)°,Z=1,Mr=11 351.63,V=4.683(7)nm3,μ=24.794mm-1,R1=0.056 4,wR2=0.150 8[I2σ(I)].化合物1是二聚结构,其中LaIII离子采用九配位畸变的单加冠四方反棱柱配位构型.     

K_3H_3[As_2W_(21)O_(69)(H_2O)]·19H_2O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.     

基于[P_2W_(15)O_(56)]~(12-)构筑块的四核铜夹心型化合物的合成、结构表征及其热稳定性

以三缺位型Dawson结构的钨磷酸盐前驱体Na12[α-P2W15O56]·24H2O与CuCl2·6H2O和Na3PO4为原料、水为溶剂,经溶液合成法合成了四核夹心型多金属氧酸盐化合物Na3H13[Cu4(H2O)2(P2W15O56)2]·72H2O(1);利用X射线单晶衍射仪、红外光谱仪、紫外光谱仪、X射线粉末衍射仪等分析了合成产物的结构,采用变温红外光谱测定了其热性质.结果表明,该化合物为三斜晶系,P-1空间群;其晶胞参数为:a=1.318 1(2)nm,b=1.345 1(2)nm,c=2.497 3(4)nm,α=78.149(3)°,β=88.242(3)°,γ=62.087(2)°.该化合物的骨架结构由两个三缺位的Dawson结构单元{P2W15O56}通过一个{Cu4O16}簇连接而成;其在350℃以下表现出一定的热稳定性.     

单核镥取代的砷钨酸盐的合成、结构及表征

以双缺位结构钨酸盐K_(14)[As_2W_(19)O_(67)(H_2O)]为多酸前驱体与LuCl_3·6H_2O和2,6-吡啶二羧酸在常规水溶液中反应,制得了一例单核镥夹心的砷钨酸盐稀土衍生物K_8H_3[Lu(H_2O)_2(As_2W_(19)O_(67))(H_2O)]·39H_2O(1),并通过X射线单晶衍射、红外光谱、热重分析等方法对该化合物进行了测试和表征.X射线单晶衍射分析表明,化合物1属于单斜晶系,P-1空间群,晶胞参数a=1.253 54(9)nm,b=1.757 83(13)nm,c=2.111 40(16)nm,α=73.326 0(10)°,β=85.721 0(10)°,γ=89.856 0(10)°.该聚阴离子是由一个镥离子镶嵌在[As_2W_(19)O_(67)(H_2O)]~(14-)({As_2W_(19)})阴离子的缺位处构成的;热重分析结果表明,化合物1阴离子结构在400℃以内是对热稳定的.     

由大环配体[As_4W_(40)O_(140)]~(28-)与Ni~Ⅱ形成的新型超大杂多化合物

在pH=4.0的水溶液中,NiCl2·6H20,NH4Cl与Na27[NaAs4W40O140].60H2O反应,得到了新的杂多砷钨酸盐(NH4)20[Na2(H2O)2Ni(H2O)5(Ni(H2O)}2As4W40O140].61H2O单晶,用X射线单晶衍射法及元素分析确定了其结构,晶体属三斜晶系,P1空间群;其晶胞参数为:a=1.33135(18),b=1.9722(3),C=3.6430(5)nm,a=78.010(2)。,β=82.145(2)。,γ=74.385(2)。,V=8.978(2)nm3,Z=2,R1=0.0512,wR2=0.0684(I>2σ).在聚阴离子[Na2(H2O)2Ni(H2O)5{Ni(H2O)}2As4W40O140]20-中,2个Ni2+和2个Na+分占大环配体[As4W40O140]28-内的4个S2空位,每个S2位提供4个Od向金属离子配位,2个Ni2+的配位数为6,两个Na+的配位数分别为5和6,另一个Ni2+处于环外,与[As4W40O140]28-的一个端基氧(Od)桥连成键,其配位数为6.     

以[As_2W_(19)O_(67)(H_2O)]~(14-)单元和Ce~(3+)构筑的二聚的砷钨酸盐的合成、结构及表征

以介稳态的K_(1 4)[As_2W_(19)O_(67)(H_2O)]为多酸前驱体与Ce Cl_3·6H_2O和2,6-吡啶二羧酸反应,采用常规水溶液合成法制得了二聚的且保持多酸前驱体[As_2W_(19)O_(67)(H_2O)]~(14-)结构骨架的多酸基稀土衍生物K_(14)H_8{Ce(H_2O)_3[As_2W_(19)O_(67)(H_2O)]}_2·48H_2O(1),并测定了其晶体结构.同时,通过红外光谱以及热分析对其进行了表征.X射线单晶结构分析表明,化合物1属于三斜晶系,P-1空间群,晶胞参数为a=1.241 13(5)nm,b=1.842 15(8)nm,c=2.193 97(9)nm,α=69.966 0(10)°,β=77.803 0(10)°,γ=77.926 0(10)°,Z=1,M_r=11 125.90,V=4.554 9(3)nm~3,μ=25.519 mm~(-1),R_1=0.045 9,wR_2=0.117 2[I2σ(I)].化合物1是二聚结构,其中Ce~(3+)离子采用八配位畸变的双加冠三棱柱配位构型.     

含有两个簇阴离子[As_8V_(14)O_(42)(SO_4)]~(6-)的金属-氧簇合物(H_2en)_6[As_8V_(14)O_(42)(SO_4)]_28H_2O的水热合成与晶体结构

合成了一种新的砷-钒-氧簇合物(H2en)6[As8V14O42(SO4)]28H2O(en为乙二胺),用元素分析、IR和TG-DTA等手段进行了表征,并用X射线衍射法测定了晶体结构。结果表明, 该晶体属单斜晶系,P21/c空间群,晶胞参数a = 20.9235(4),b = 11.9382(2),c = 43.5783(6) 牛琤 = 102.13,V = 10642.1(3) ?,Z = 4,Mr = 4678.01,Dc = 2.920 g/cm3,F(000) = 8944,m = 7.437 mm-1,R = 0.0735,wR = 0.1361。结构测定表明,结构中2个簇阴离子{[As8V14O42(SO4)]6-}与有机铵阳离子[H2en]2+之间靠静电作用相结合,同时与H2O通过氢键构成无限的三维骨架结构。     

夹心型杂多化合物Na_9[CeW_(10)O_(36)]·34H_2O的合成及晶体结构

在pH≈6.5及NaAsO_2和Co(NO_3)_3·6H_2O存在下,Na_2WO_4·2H_2O 与Ce (NO_3)_3·6H_2O反应,得到了Na_9[CeW_(10)-O_(36)]·34H_2单晶。用元素分析 及X射线单晶衍射法确定了其组成与结构,晶体学数据为：a = 1.3010(5) nm, b = 1.3072(5) nm, c = 1.9962(8) nm, α= 101.073(7) °, β = 104.411(5) ° γ = 90.473(4) °, V = 3.221(2) nm~3,空间群P1,V=3.211(2)nm~3, Z = 4, 最终R因子[1>2σ(I)]R_1=0.0424, wR_2 = 0.0549, R因子（全部数据）R_1=0. 1357, wR_2 = 0.0808.[CeW_(10)O(36)]~(9-)具有D_(4d)对称性。     

[Co(enMe)_3]_2[As_8V_(14)O_(42)(H_2O)]·10H_2O的水热合成、性质和晶体结构

合成了一种新的砷-钒-氧簇合物[Co(enMe)3]2[As8V14O42(H2O)]10H2O(enMe为1,2-丙二胺),用元素分析、IR和TGA-DTA等进行了表征,并用X射线衍射法测定了晶体结构。结果表明,该晶体属单斜晶系,C2/c空间群,晶胞参数a=28.990(7),b=15.540(6),c=22.77(1),b=131.24(4),Mr=2744.68,V=7714(7)3,Z=4,F(000)=5232,m(MoKa)=7.239mm-1,Dc=2.363g/cm3,R=0.069,Rw=0.073。结构测定表明,结构中簇阴离子[As8V14O42(H2O)]4-与配位阳离子[Co(enMe)3]2+之间靠静电作用相结合,同时通过氢键构成无限的三维骨架结构。     

硅钨酸盐[H_2bpy][H_2bbpy][α-SiW_(12)O_(40)]·2H_2O的合成与结构表征

以Na10[A-α-SiW9O34].18H2O、CuCl2.2H2O、EuCl3、联咪唑、4,4′-联吡啶为原料,利用水热法合成了有机-无机复合Keggin结构硅钨酸盐[H2bpy][H2bbpy][α-SiW12O40].2H2O[bpy=4,4′-bipyridine,bbpy=N-(2-(4,4′-bipyridyl))-4,4′-bipyridine],并借助元素分析、红外光谱和X射线单晶衍射对其组成和结构进行了表征.结果表明,标题化合物属于单斜晶系,P2(1)/c空间群,晶胞参数为:a=1.149 92(13)nm,b=2.137 6(3)nm,c=2.248 2(3)nm,β=98.406(2)°,V=5.466 7(111)nm3,Z=4,Dc=4.109g/cm3,GOOF=1.038,R1=0.057 5,wR2=0.118 4.其分子由1个饱和的硅钨酸盐[α-SiW12O40]4-阴离子,1个游离的双质子化[H2bbpy]2+阳离子,1个游离的双质子化[H2bpy]2+阳离子和2个结晶水分子组成.值得指出的是,4,4′-联吡啶分子在水热条件下发生反应,形成N-(2-(4,4′-联吡啶基))-4,4′-联吡啶.     

Dititanium-containing 19-tungstodiarsenate(III) [Ti2(OH)2As2W19O67(H2O)]8-: synthesis, structure, electrochemistry, and oxidation catalysis

The dititanium-containing 19-tungstodiarsenate(III) [Ti(2)(OH)(2)As(2)W(19)O(67)(H(2)O)](8-) (1) has been synthesized and characterized by IR, TGA, elemental analysis, electrochemistry, and catalytic studies. Single-crystal X-ray analysis was carried out on Cs(8)[Ti(2)(OH)(2)As(2)W(19)O(67)(H(2)O)].2CsCl.12H(2)O (Cs-1), which crystallizes in the monoclinic system, space group P2(1)/m, with a=12.7764(19), b=19.425(3), c=18.149(3) A, beta=110.234(3) degrees, and Z=2. Polyanion 1 comprises two (B-alpha-As(III)W(9)O(33)) Keggin moieties linked through an octahedral {WO(5)(H(2)O)} fragment and two unprecedented square-pyramidal {TiO(4)(OH)} groups, leading to a sandwich-type structure with nominal C(2v) symmetry. Synthesis of 1 was accomplished by reaction of TiOSO(4) and K(14)[As(2)W(19)O(67)(H(2)O)] in a 2:1 molar ratio in aqueous, acidic medium (pH 2). Polyanion 1 could also be isolated as a tetra-n-butyl ammonium (TBA) salt, {(n-C(4)H(9))(4)N}(5)H(3)[Ti(2)(OH)(2)As(2)W(19)O(67)(H(2)O)] (TBA-1). TBA-1 was studied by cyclic voltammetry in acetonitrile (MeCN) solutions containing 0.1 M LiClO(4) and compared with the results obtained with Cs-1 in aqueous media. In MeCN, the Ti(IV) and W(VI) waves could not be separated distinctly. An important adsorption phenomenon on the glassy carbon working electrode was encountered both in cyclic voltammetry and in controlled potential electrolysis and was confirmed by Electrochemical Quartz Crystal Microbalance (EQCM) studies on a carbon film. TBA-1, dissolved in MeCN, reacts with H(2)O(2) to give peroxo complexes stable enough for characterization by UV-visible spectroscopy, cyclic voltammetry, and EQCM. TBA-1 shows high catalytic activity (TOF=11.3 h(-1)) in cyclohexene oxidation with aqueous H(2)O(2) producing products typical of a heterolytic oxidation mechanism. The stability of TBA-1 under turnover conditions was confirmed by using IR, UV-visible spectroscopy as well as cyclic voltammetry.     

Utilizing the adaptive polyoxometalate [As2W19O67(H2O)](14-) to support a polynuclear lanthanoid-based single-molecule magnet

Five members of a new family of polyoxometalate (POM)-ligated tetranuclear rare earth metal complexes have been synthesized and characterized. These compounds have the general formula (HDABCO)(8)H(5)Li(8)[Ln(4)As(5)W(40)O(144)(H(2)O)(10)(gly)(2)]·25H(2)O [Ln = Gd (1), Tb (2), Dy (3), Ho (4) and Y = (5), HDABCO = monoprotonated 1,4-diazabicyclooctane, gly = glycine] and were synthesized from the preformed POM precursor [As(2)W(19)O(67)(H(2)O)](14-). The structure is comprised of two {As(2)W(19)O(68)} building blocks linked by a unit containing four rare earth ions and two additional tungsten centers, with the two glycine ligands playing a key bridging role. Two crystallographically distinct rare earth ions are present in each complex, both of which possess axially compressed, approximate square antiprismatic coordination geometry. The variable-temperature magnetic susceptibility profiles for 2-4 are dominated by population/depopulation of the M(J) sublevels of the relevant ground terms, and fitting of the data has afforded the ligand field parameters in each case, from which the energies of the M(J) sublevels can be calculated. Alternating current magnetic susceptibility data have revealed the onset of slow magnetic relaxation for 3, with the energy barrier to magnetization reversal determined to be 3.9(1) K. As for other lanthanoid complexes that display slow magnetic relaxation, this energy barrier is due to the splitting of the M(J) sublevels of the Dy(3+) ions such that the ground sublevel has a relatively large |M(J)| value, thereby affording Ising-type magnetic anisotropy. This complex is thus the first POM-supported polynuclear lanthanoid-based SMM. Simulation of the W-band EPR spectrum of 1 has afforded the spin Hamiltonian parameters for this species, while the X-band EPR spectrum of 3 indicates the presence of a non-negligible fourth-order transverse component of the anisotropy, which is responsible for the small effective energy barrier observed for 3 and the absence of slow magnetic relaxation for 4.     

Synthesis, crystal structure, and thermal stability of 1D coordination polymer [Zn(BDOA)(Py)2(H2O)] n

A new coordination polymer, [Zn(BDOA)(Py)₂(H₂O)] _n (I) (BDOA = benzene-1,4-dioxylacetate, Py = pyridine), has been prepared via self-assembly of benzene-1,4-dioxylacetate with zinc nitrate under mild conditions and characterized by IR spectra, elemental analysis and X-ray diffraction single-crystal analysis. The complex crystallizes in the monoclinic system, space group C2/c with a = 15.5751(9), b = 6.0898(4), c = 21.7133(13) Å, V = 1991.9(2) ų, β = 104.719(1)°, Z = 4. The zinc atoms are bridged by BDOA ligand, forming a one-dimensional chain along the z axis. A two-dimensional layer structure is formed by the intermolecular hydrogen bonds. The thermal decomposition profile of the complex is reported as well.     

邻香草醛氧钒配合物的合成和晶体结构

钒是人体所必需的微量元素,钒化合物是新一代潜在的抗糖尿病药物。我们合成了邻香草醛氧钒配合物[VO(o-van)2(H2O)],并通过红外光谱,元素分析和X-射线单晶衍射等手段确定了其结构。     

新型化合物[Co(en)3]2·2H3O·[As8V14O42(HPO4)]·2H2O晶体的水热合成与表征

近年来, 聚氧酸盐化学发展迅速,有些聚氧酸盐作为催化剂已经实现了工业化,由于聚氧酸盐在结构上具有特殊性,因而其在制药及材料科学方面具有潜在的应用价值,因而引起人们的关注[1～10].     

单核铜配合物[Cu~(II)(HIPP)(pydc)(H_2O)]的合成和晶体结构

用溶剂热合成方法合成了一个单核铜配合物CuII(HIPP)(pydc)(H2O),采用元素分析法和X射线单晶衍射法对该配合物的组成和结构进行了表征.配合物CuII(HIPP)(pydc)(H2O)属于正交晶系,空间群是Pbca.a=0.663 93(18)nm,b=2.062 2(6)nm,c=2.619 1(7)nm,α=90°,β=90°,γ=90°,V=3.585 9(17)nm3,Z=8,ρc=1.693g·cm-3,F(000)=1 864,GOF=0.882,R1=0.037 4,wR2=0.111 8[I2σ(I)].中心铜原子与配体脱质子2,6-吡啶二甲酸的2个羧基氧原子和1个氮原子、HIPP的1个氮原子和1个氧原子及1个水分子中的氧原子形成六配位的变形八面体.结构分析表明晶体中分子间含有氢键.