配合物Cu(phen)2 (dca)2的合成及晶体结构

合成了配合物Cu(phen)2 (dca)2(phen=C12H8N2为1,10-邻菲啰啉,dca-为二氰基氨基阴离子),用IR对其结构进行了初步表征,并测定了配合物的晶体结构.该晶体属单斜晶系,空间群为P21/c;晶胞参数a=0.8869(2)nm,b=1.4691(2)nm,c=1.9298(2)nm,β=100.90(1)°;V=2.4691(8)nm3,Z=4,F(000)=1132.00,Dc=1.496g/cm3,R=0.051,RW=0.068.中心铜(Ⅱ)离子分别与两个phen中的四个N原子和两个dca-的两个N原子配位,形成六配位的变形八面体结构.     

聚(苯乙烯-丙烯酸)载体铁邻菲啰啉(5-硝基邻菲啰啉)配合物的合成及其对丁二烯聚合的催化活性

合成了不同邻菲啰啉(phen)含量的聚(苯乙烯-丙烯酸)载体铁邻菲啰啉配合物(SAAC·Fe·phen)和不同5-硝基邻菲啰啉(Nphen)含量的聚(苯乙烯-丙烯酸)载体铁5-硝基邻菲啰啉配合物(SAAC·Fe·Nphen)。元素分析和红外结果证明SAAC·Fe·phen具有下面的结构:SAAC·Fe·phen-(i-Bu)_3Al二元体系的催化效率是SAAC·Fe-phen-(i-Bu)_3Al三元体系的2倍,是小分子铁的400倍。在SAAC·Fe·phen和SAAC·Fe·Nphen体系中,当phen(或N pnen)/Fe的摩尔比为0.7左右时催化活性最高。催化活性随着Al/Fe摩尔比的增大而升高,但当Al/Fe摩尔比大于70以上活性趋于恒定,和小分子铁催化荆相比这种高分子铁催化剂可以提高聚合温度。     

磺基水杨酸·邻菲咯啉合铜三元配合物的合成与表征

合成了磺基水杨酸·邻菲咯啉合铜酸钠和磺基水杨酸·5 硝基邻菲咯啉合铜酸钠配合物,用元素分析、红外光谱、紫外可见光谱、热重分析对配合物的组成和结构进行了表征.     

过渡金属离子与3-氟邻苯二甲酸和1,10-邻菲啰啉配合物的合成、结构及性质

过渡金属离子与3-氟邻苯二甲酸（H₂Fpht）、1,10-邻菲啰啉（phen）通过水热反应得到了5个配合物：[M（Fpht）（phen）（H₂O）₃]·H₂O（M=Ni 1,Co 2）,[Cu（Fpht）（phen）（H₂O）]·H₂O（3）,[M（Fpht）（phen）（H₂O）]·H₂O（M=Zn 4,Cd 5）。通过X-射线单晶衍射分析、元素分析、红外分析、荧光分析以及差热-热重分析对配合物进行了表征。配合物1和2为单核分子,中心离子Ni（Ⅱ）和Co（Ⅱ）与3-氟邻苯二甲酸根的1个氧原子,1,10-邻菲啰啉的2个氮原子以及3个配位水分子的3个氧原子配位,形成六配位的扭曲八面体构型。配合物3为Z字形一维链状结构。中心Cu（Ⅱ）离子与2个3-氟邻苯二甲酸根的2个氧原子,1个1,10-邻菲啰啉的2个氮原子以及水分子的1个氧原子配位,形成四方锥构型。配合物4和5具有相似的一维螺旋结构,中心Zn（Ⅱ）和Cd（Ⅱ）离子与2个3-氟邻苯二甲酸根的3个氧原子、1,10-邻菲啰啉的2个氮原子以及水分子中的1个氧原子配位,形成扭曲的八面体构型。     

过渡金属离子与3-氟邻苯二甲酸和1,10-邻菲啰啉配合物的合成、结构及性质

过渡金属离子与3-氟邻苯二甲酸(H2Fpht)、1,10-邻菲啰啉(phen)通过水热反应得到了5个配合物:[M(Fpht)(phen)(H2O)3]·H2O(M=Ni 1,Co 2),[Cu(Fpht)(phen)(H2O)]·H2O(3),[M(Fpht)(phen)(H2O)]·H2O(M=Zn 4,Cd 5)。通过X-射线单晶衍射分析、元素分析、红外分析、荧光分析以及差热-热重分析对配合物进行了表征。配合物1和2为单核分子,中心离子Ni(Ⅱ)和Co(Ⅱ)与3-氟邻苯二甲酸根的1个氧原子,1,10-邻菲啰啉的2个氮原子以及3个配位水分子的3个氧原子配位,形成六配位的扭曲八面体构型。配合物3为Z字形一维链状结构。中心Cu(Ⅱ)离子与2个3-氟邻苯二甲酸根的2个氧原子,1个1,10-邻菲啰啉的2个氮原子以及水分子的1个氧原子配位,形成四方锥构型。配合物4和5具有相似的一维螺旋结构,中心Zn(Ⅱ)和Cd(Ⅱ)离子与2个3-氟邻苯二甲酸根的3个氧原子、1,10-邻菲啰啉的2个氮原子以及水分子中的1个氧原子配位,形成扭曲的八面体构型。     

Tb(Ⅲ)-氨基多膦酸-邻菲咯啉三元配合物的溶液荧光

氨基多膦酸类配体如乙二胺四甲基次膦酸(EDTP)等与氨基多羧酸类配体具有相似的骨架结构 ,只是后者分子中的羧酸根-COOH被前者的膦酸根-PO3H2所取代.     

α,β—不饱和酸铜与1,10—邻菲绕啉三元配合物的合成,表征…

合成了丙烯酸铜和α－甲基丙烯酸铜与１，１０－邻菲绕啉形成的三元配合物，通过元素分析，红外光谱，热谱等数据对配合物进行了表征，测定了Ｃｕ（Ｃ４Ｈ５Ｏ２）２（ｐｈｅｎ）．Ｈ２Ｏ的晶体结构，配合物的组成为ＣｕＬ２（ｐｈｅｎ）．Ｈ２Ｏ（Ｌ＝ＣＨ２＝ＣＨ－ＣＯＯ＾－，ＣＨ２＝Ｃ（ＣＨ３）－ＣＯＯ＾－），结构为畸变的四方锥形，属单斜晶系，Ｐ２１／ｎ群，晶胞参数：ａ＝０．７３２２ｎｍ，ｂ＝１．７９４８ｎｍ，ｃ＝     

多核过渡金属配合物的磁性研究

本文以双核Cu(II)配合物作为磁性研究的典型例子,扼要地介绍了磁性离子的基本性质,多原子桥联多核配合物的变温磁化率、超交換相互作用及其机理的理论模型,并对近年来多核配合物的磁性研究的某些进展作了简要评述。     

呋喃甲酰基吡唑啉酮铅三元配合物吸附波的研究

在pH值为3.75的HAc-NaAc介质中, 测得1-苯基-3-甲基-4-(α-呋喃甲酰基)吡唑啉酮-5(HPMαFP)与邻菲啰啉(phen)合铅三元配合物的灵敏极谱波(-0.51 V (vs SCE))。铅浓度在0.02～10 μg·mL^-1范围内与峰电流分段呈良好的线性关系,检测下限为0.002 μg·mL^-1。采用多种电化学方法研究了极谱波的性质和电极反应机理，证明-0.51 V处的极谱波为多元配合物吸附波，峰电流由中心离子Pb(Ⅱ)还原产生。根据直线法测得多元配合物组成为n_Pb²⁺∶n_phen∶n_HPMαFP=1∶1∶1，表观稳定常数为5.44×10⁸。此体系用于粗盐、蔗糖和化妆品中铅测定，标准回收率98.5%～102.5%。     

Zero- and One-dimensional Organic-inorganic Hybrid Compounds Based on Monovacant Keggin Polyoxotungstatesa

Two new organic-inorganic hybrid mono-transition-metal-substituted polyoxometalates [Ni(2,2'-bipy)3]3[Ni(H2O)SiW11O39]·11H2O 1 and [Cu(dien)(H2O)][Cu(dien)(H2O)2]2-[CuSiW11O39]·5.5H2O 2 (2,2'-bipy = 2,2'-bipyridine, dien = diethylenetriamine) have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, magnetic properties, and IR spectrum. Crystal data for 1: monoclinic, space group P21/n, a = 17.492(3), b = 33.481(5), c = 20.493(3) A, β = 101.894(3)°, Dc = 2.563 mg/A3, F(000) = 8440,μ = 11.454 mm-1 and Z = 4; and those for 2: monoclinic, space group P21/n, a = 11.114(3), b = 22.803(7), c = 22.468(7) A, β = 97.896(6)°, Dc = 4.036 mg/A3, F(000) = 6140,μ = 23.942 mm-1 and Z = 4. The study on the magnetic susceptibility of 2 demonstrates the presence of ferromagnetic interaction.     

Hydrothermal synthesis and structures of two novel chain-like heteropolymolybdate formed by Keggin cluster units

Two novel heteropolymolybdate, [H₂bpy]₂ [Hbpy] [PCuMo₁₁O₃₉]·H₂O 1 and [H₂bpy]₂ [Hbpy] [PZnMo₁₁O₃₉]·2.75H₂O 2, have been prepared under mild hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. The two compounds are isostructural and crystallize in the monoclinic space group P2(1)/n (No. 14) with a=13.440(3) Å, b=26.660(5) Å, c=15.240(3) Å, β=99.55(3)°, and Z=4 for the compound 1, and a=13.610(3) Å, b=26.781(5) Å, c=15.205(3) Å, β=100.40(3)°, and Z=4 for the compound 2. Compound 1 and 2 exhibit a zigzag chain structure in which Keggin anions are connected through a common oxygen atom. They are the first characterized compounds containing 1D chains of transition-metal substituted Keggin heteropolymolybdate. Other characterizations by elemental analysis, IR, EPR, TG, and XRPD are also described.     

Trapping the δ Isomer of the Polyoxometalate‐Based Keggin Cluster with a Tripodal Ligand

We report the synthesis, structural, and electronic characterization of the theoretically predicted, but experimentally elusive δ‐isomer of the Keggin polyoxometalate polyanion. A family of δ‐Keggin polyoxoanions of the general formula, (TEA)H_pNa_q [H₂M₁₂(XO₄)O₃₃(TEA)]?r H₂O where p, q, r=[2,3,8] for 1 and [4,1,4] for 2 were isolated by the reaction of tungstate(VI) and vanadium(V) with triethanolammonium ions (TEAH), acting as a tripodal ligand grafted to the surface of the cluster thereby stabilizing the polyanionic δ‐Keggin archetype. The δ‐Keggin species were characterized by single‐crystal X‐ray diffraction, FT‐IR, UV/Vis, NMR, and ESI‐MS spectrometry. Electronic structure and structure–stability correlations were evaluated by means of DFT calculations. The compounds exhibited multi‐electron transfer and reversible photochromic properties by undergoing single‐crystal‐to‐single‐crystal (SC–SC) transformations accompanied with color changes under light.     

Isomerization of Keggin Al13 Ions Followed by Diffusion Rates

The solution chemistry of aluminum has long interested scientists due to its relevance to materials chemistry and geochemistry. The dynamic behavior of large aluminum–oxo‐hydroxo clusters, specifically [Al₁₃O₄(OH)₂₄(H₂O)₁₂]⁷⁺ ( Al₁₃ ), is the focus of this paper. ²⁷Al NMR, ¹H NMR, and ¹H DOSY techniques were used to follow the isomerization of the ?‐Al₁₃ in the presence of glycine and Ca²⁺ at 90 °C. Although the conversion of ?‐Al₁₃ to new clusters and/or Baker–Figgis–Keggin isomers has been studied previously, new ¹H NMR and ¹H DOSY analyses provided information about the role of glycine, the ligated intermediates, and the mechanism of isomerization. New ¹H NMR data suggest that glycine plays a critical role in the isomerization. Surprisingly, glycine does not bind to Al₃₀ clusters, which were previously proposed as an intermediate in the isomerization. Additionally, a highly symmetric tetrahedral signal (δ=72 ppm) appeared during the isomerization process, which evidence suggests corresponds to the long‐sought α‐Al₁₃ isomer in solution.     

Isomerization and Antiacidolysis Properties of Molybdic Heteropoly Blues with Keggin Structure

For eight kinds of acidic potassium salts of hetcropoly blues which have not been reported in literature,the isomeri/.ation reaction in solution for these two-and four-electron hcteropoly blue solids were investigated by means of polarograms,cyclic voltammetry,31P NMR and X-ray diffraction methods.The heteropolynier of PMo12 and AsMo12 converte to their β-isomers during isomerization reaction which were found to have antiacidolysis property.     

27Al NMR diffusometry of Al13 Keggin nanoclusters

Although nanometer-sized aluminum hydroxide clusters (i.e., ϵ-Al₁₃, [Al₁₃O₄(OH)₂₄(H₂O)₁₂]⁷⁺) command a central role in aluminum ion speciation and transformations between minerals, measurement of their translational diffusion is often limited to indirect methods. Here, ²⁷Al pulsed field gradient stimulated echo nuclear magnetic resonance (PFGSTE NMR) spectroscopy has been applied to the AlO₄ core of the ϵ-Al₁₃ cluster with complementary theoretical simulations of the diffusion coefficient and corresponding hydrodynamic radii from a boundary element-based calculation. The tetrahedral AlO₄ center of the ϵ-Al₁₃ cluster is symmetric and exhibits only weak quadrupolar coupling, which results in favorable T₁ and T₂ ²⁷Al NMR relaxation coefficients for ²⁷Al PFGSTE NMR studies. Stokes–Einstein relationship was used to relate the ²⁷Al diffusion coefficient of the ϵ-Al₁₃ cluster to the hydrodynamic radius for comparison with theoretical simulations, dynamic light scattering from literature, and previously published ¹H PFGSTE NMR studies of chelated Keggin clusters. This first-of-its-kind observation proves that ²⁷Al PFGSTE NMR diffusometry can probe symmetric Al environments in polynuclear clusters of greater molecular weight than previously considered.     

Micro- and nanocomposites of Keggin heteropolymetalates in cellulose esters

Composites of Keggin heteropolymetalates have been prepared and characterized by SEM, XPS, ³¹P-magic angle spinning/nuclear magnetic resonance and differential scanning calorimetry. The phosphotungstic acid and phosphomolybdic acid form nanocomposites where the oxocluster structure is preserved and is highly dispersed over the material, probably inserted between the polymeric chains. Phosphovanadotungstic clusters suffer partial decomposition during composite formation, resulting in a biphasic microcomposite. The decomposition product, phosphotungstic acid presents surface segregation as shown by comparison of XPS and nuclear magnetic resonance results. Copyright © 2002 John Wiley & Sons, Ltd.     

两个多钒盖帽的Keggin型多铌钒酸盐衍生物的水热合成与表征

通过水热方法合成了2个由多铌酸盐和过渡金属配合物形成的有机-无机杂化配合物[Cu(TETA)]₄[VNb₁₂(VO)₄O₄₀][OH]·10H₂O(1)和[Cu(TETA)]₄[VNb₁₂(VO)₆O₄₀][OH]₅·5H₂O(2)(TETA=三亚乙基四胺). 化合物1和2的多阴离子分别是由4个{VO₅}帽和6个{VO₅}帽加盖在Keggin型多铌酸盐的方形缺口上形成的, 它们通过多酸阴离子中Nb-O_t (O_t =端氧)与[Cu(TETA)]²⁺配合物的金属中心配位构筑形成三维结构. 价键计算结果表明, Keggin中心的钒为+5价, 帽位的钒为+4价, X射线光电子能谱分析(XPS)结果也证实了这一结论. 通过单晶X射线衍射分析、红外光谱(IR)、粉末X射线衍射(PXRD)、热重(TG)分析和元素分析对这2个化合物的结构和性质进行了表征.     

Two Keggin Templated Supramolecular Compounds by Exerting the Chelate and Linking Dual Roles of the Ligand 2, 2′‐Biimidazole

Two new Keggin templated supramolecular compounds, [Zn₂(H₂biim)₅(SiM₁₂O₄₀)] · 4H₂O [M = W ( 1 ), Mo ( 2 )] (H₂biim = 2, 2′‐biimidazole), were synthesized under hydrothermal conditions by using the ligand 2, 2′‐biimidazole. They were characterized by single‐crystal X‐ray diffraction, elemental analyses, IR and photoluminescence spectroscopy as well as cyclic voltammetry. The two isostructural compounds are constructed by two discrete supramolecular moieties: the inorganic chains consist of Keggin anions and metal‐organic chains constructed by [Zn₂(H₂biim)₅]⁴⁺ subunits. In the dinuclear [Zn₂(H₂biim)₅]⁴⁺ subunit, the H₂biim ligands exhibit a dual role, chelating and linking. The metal‐organic chains further construct a 3D supramolecular framework with channels, in which the Keggin‐based inorganic chains are accommodated. The electrochemical behaviors of compounds 1 and 2 bulk‐modified carbon paste electrodes ( 1 ‐CPE, 2 ‐CPE) were studied.