【作者】 肖利娜；

【导师】 徐家宁； 崔小兵；

【作者基本信息】 吉林大学 ， 无机化学， 2014， 博士

【摘要】 本论文主要致力于新的金属-氧簇合物的合成、结构和性能研究。在酸性条件下，选用不同的反应体系，通过水热方法主要合成出33个结构新颖、性能优异的非经典金属-氧簇合物，其全部为首次合成。这33个化合物分别为：1.[V16O39Cl][Fe(Phen)3]3·7.5H2O (1)2.[(HSiMo12O40)(H4,4’-bpy)2][(H4,4’-bpy)(H2O)2]·2H2O (2)3.[Cu2(4,4’-bpy)2][HPMo12O40]·(C5H6N2)(3)4.[(HSiW12O40)(H4,4’-bpy)2][(H4,4’-bpy)(H2O)2]·2H2O (4)5.[(SiW12O40)(H4,4’-bpy)4]·(4,4’-bpy)·2H2O (5)6.[H4SiW12O40](2,2’-bpy)4(6)7.[Cu3(4,4’-bpy)3][HSiW12O40]·Im (7)8.[Cu(Phen)(4,4’-bpy)(H2O)]2[PW12O40]·(4,4’-bpy)(8)9.[Mo8V7O42][Cu(2,2’-bpy)2]2[Cu(2,2’-bpy)]·2H3O (9)10.[H24,4’-bpy][PMo12Sb2O40]·6H2O (10)11.[Him]2[PMo12Sb2O40]·H2O (11)12.[H3(DABCO)2][PMo12Sb2O40]·2H2O (12)13.[Mn(phen)3][PMo12Sb2O40](13)14.[Cu(Phen)2]2[PMo12Sb2O40](14)15.[Cd(bpy)4(H2O)2][PMo12Sb2O40]·bpy·2H2O (15)16.{[PMo12Sb2O40][Cu(Im)2]2}·Im (16)17.{[PMo12Sb2O40][(Cd(Phen)2)2Cl]}(17)18.[Cu(Phen)2]4[Cu4I3(Phen)4][BW12O40]·3H2O (18)19.[Cu(Phen)2]4[Cu4I3(Phen)4][PW12O40]·3H2O (19)20.[Cu(Phen)2]4[Cu5Cl4(Phen)4][AlW12O40]·4H2O (20)21.[Cu(Phen)2]4[Cu5Cl4(Phen)4][PW12O40]·4H2O (21)22.[Cu(Phen)2]4[Cu5Cl4(Phen)4][BW12O40]·2H2O (22)23.[Cu(Phen)2]4[Cu5Br4(Phen)4][AlW12O40]·6H2O (23)24.[Cu(Phen)2]4[Cu5Br4(Phen)4][PW12O40]·4H2O (24)25.[Cu(Phen)2]4[Cu5Br4(Phen)4][BW12O40]·8H2O (25)26.[HAlW12O40]][Co(Phen)2(H2O)]2·4H2O (26)27.[PW12O40][Ag4(bzmd)2](27)28.[Ag6(bzmd)2][SiW12O40](28)29.[Cu3(4,4’-bpy)3][PMo12O40]·(C5H6N2)(29)30.[HPW12O40][Cd(2,2’-bpy)3](2,2’-bpy)(30)31.[SiW12O40][Cd(2,2’-bpy)2]2(31)32.[Cu(Phen)2]2[Cu11Cl7(Phen)8][PW12O40])(32)33.{[PMo12V2O42][Cu(enMe)2][Cu(enMe)2(H2O)]}[Cu(enMe)2(H2O)](33)研究了过渡金属、有机配体和反应体系的pH值等因素对反应产物的影响。在确定其单晶结构的基础上，对这些化合物进行了元素分析、红外(IR)、紫外(UV-Vis)、电子顺磁共振(EPR)、荧光、X-射线光电子能谱(XPS)以及X-射线粉末衍射(XRD)等多种表征，还研究了部分化合物的热稳定性、电化学及磁学性能，为进一步探索金属-氧簇合物的功能特性与结构之间的关系，进而展开应用方面的研究提供了物质基础。在本论文中我们将重点讨论前25个化合物：一、钒-氧簇合物利用水热方法合成了1个钒-氧簇合物(化合物1)。化合物1是新的基于[V16O39Cl]6和过渡金属配离子[Fe(Phen)3]2+的簇合物。[V16O39Cl]6是首例由15个VO5四角锥和1个VO4四面体组成的簇阴离子，罕见的是VO4四面体中含有两个端氧原子。详细分析表明，化合物1中存在着强烈的O-H···O氢键和C-H···O氢键作用，通过氢键作用，化合物1形成3-D超分子结构。对化合物1进行了X-射线单晶结构分析、元素分析、IR、XRD、UV-Vis、XPS表征及热重分析，并对化合物1进行了磁性测定，表现为反铁磁性相互作用。二、钼-氧簇合物利用水热方法合成了两个钼-氧簇合物(化合物2-3)。化合物2中存在着两种不同的1-D超分子链，有趣的是这两种链互相交织，形成2-D超分子层状结构。进一步的研究表明，化合物2中还存在着C-H···O氢键作用，这些氢键作用增强了化合物2的稳定性，并且将簇单元、有机配体和水分子连接成3-D超分子结构。化合物3通过金属氧簇阴离子、过渡金属离子和有机配体的相互作用形成新的连接方式为POM-M-L-M-POM的1-D链状结构。对化合物2-3进行了X-射线单晶结构分析、元素分析、IR、UV-Vis、XRD、XPS表征及热稳定性的研究，并对化合物3的荧光及电化学性能进行了测定。三、钨-氧簇合物通过水热技术合成了5个钨-氧簇合物(化合物4-8)。其中化合物4-6是基于金属-氧簇阴离子和纯有机配体的化合物。通过氢键作用，化合物4形成新的2-D超分子层状结构，化合物5展现出新的1-D超分子双链状结构，2,2’-bpy作为双桥将化合物6连接成1-D超分子链状结构。罕见的是化合物7-8通过金属-氧簇阴离子、过渡金属离子和有机配体的相互作用形成新的连接方式为POM-M-L-M-POM的骨架材料(POMMOF)。化合物7展现出新颖的3-D骨架结构，而化合物8则展现出独特的2-D层状结构，值得注意的是化合物8的过渡金属配合物中的过渡金属离子同时与两种有机配体配位。对以上化合物进行了X-射线单晶结构分析、元素分析、IR、UV-Vis、XRD、荧光、XPS表征及热稳定性的研究，并对化合物7-8的电化学性能进行了测定。四、二帽Keggin型金属-氧簇合物通过水热技术合成了9个二帽Keggin型金属-氧簇合物(化合物9-17)。其中化合物9代表了二帽Keggin型簇阴离子与混价过渡金属配合物通过桥氧和端氧相连形成的具有三支撑结构的分立簇合物。化合物10-12代表了基于不同有机配体和二帽Keggin型金属-氧簇单元{PMo12Sb2O40}的化合物，这些化合物通过氢键作用形成独特的超分子链状结构。化合物13-15是基于{PMo12Sb2O40}和过渡金属配合物的具有分立结构的化合物。有趣的是化合物13和14中的POMs分别被堆积成面心立方格子和体心立方格子的形状，化合物15通过氢键作用形成新颖的3-D超分子结构。更有趣的是化合物16中的簇阴离子[PMo12Sb2O40]2-作为一个多齿配体与四个过渡金属配离子[Cu(Im)2]+TMCs配位，从而形成独特的1-D链状结构。罕见的是化合物17中含有一个蝴蝶型的金属卤素簇{Cd(Phen)2]2Cl}3+，这个金属卤素簇作为桥将簇阴离子[PMo12Sb2O40]3-连接成1-D链状结构，这是首例基于簇单元{PMo12Sb2O40}、过渡金属配合物和卤素离子的具有拓展结构的化合物。对以上化合物进行了X-射线单晶结构分析、元素分析、IR、UV-Vis、XRD、荧光、XPS表征及热稳定性的研究。并测定了化合物9的变温磁化率，表现为反铁磁性相互作用。五、基于金属卤素簇和金属-氧簇的化合物通过水热技术合成了8个基于金属卤素簇和金属-氧簇阴离子的化合物(化合物18-25)。其中化合物18和19是同构的，并且这两个化合物中的金属卤素簇是七核的。同构的化合物20-25代表了新的基于九核金属卤素簇和金属-氧簇阴离子的化合物，除此之外，化合物20-22中含有氯离子，而化合物18-19和23-25中的卤素离子则分别是碘离子和溴离子。对以上化合物进行了X-射线单晶结构分析、元素分析、IR、UV-Vis、XRD和XPS表征，并研究了化合物的热稳定性。更多还原

【Abstract】 This thesis mainly focuses on the syntheses, structures and properties of novelmetal-oxygen clusters (POMs). Under acid condition, choosing different reactionsystem, we have successfully hydrothermal synthesized33novel non-classical metal-oxygen clusters with novel structures and excellent properties. They were allsynthesized for the first time. The33compounds are as folows:1.[V16O39Cl][Fe(Phen)3]3·7.5H2O (1)2.[(HSiMo12O40)(H4,4’-bpy)2][(H4,4’-bpy)(H2O)2]·2H2O (2)3.[Cu2(4,4’-bpy)2][HPMo12O40]·(C5H6N2)(3)4.[(HSiW12O40)(H4,4’-bpy)2][(H4,4’-bpy)(H2O)2]·2H2O (4)5.[(SiW12O40)(H4,4’-bpy)4]·(4,4’-bpy)·2H2O (5)6.[H4SiW12O40](2,2’-bpy)4(6)7.[Cu3(4,4’-bpy)3][HSiW12O40]·Im (7)8.[Cu(Phen)(4,4’-bpy)(H2O)]2[PW12O40]·(4,4’-bpy)(8)9.[Mo8V7O42][Cu(2,2’-bpy)2]2[Cu(2,2’-bpy)]·2H3O (9)10.[H24,4’-bpy][PMo12Sb2O40]·6H2O (10)11.[Him]2[PMo12Sb2O40]·H2O (11)12.[H3(DABCO)2][PMo12Sb2O40]·2H2O (12)13.[Mn(phen)3][PMo12Sb2O40](13)14.[Cu(Phen)2]2[PMo12Sb2O40](14)15.[Cd(bpy)4(H2O)2][PMo12Sb2O40]·bpy·2H2O (15)16.{[PMo12Sb2O40][Cu(Im)2]2}·Im (16)17.{[PMo12Sb2O40][(Cd(Phen)2)2Cl]}(17)18.[Cu(Phen)2]4[Cu4I3(Phen)4][BW12O40]·3H2O (18)19.[Cu(Phen)2]4[Cu4I3(Phen)4][PW12O40]·3H2O (19)20.[Cu(Phen)2]4[Cu5Cl4(Phen)4][AlW12O40]·4H2O (20)21.[Cu(Phen)2]4[Cu5Cl4(Phen)4][PW12O40]·4H2O (21)22.[Cu(Phen)2]4[Cu5Cl4(Phen)4][BW12O40]·2H2O (22)23.[Cu(Phen)2]4[Cu5Br4(Phen)4][AlW12O40]·6H2O (23) 24.[Cu(Phen)2]4[Cu5Br4(Phen)4][PW12O40]·4H2O (24)25.[Cu(Phen)2]4[Cu5Br4(Phen)4][BW12O40]·8H2O (25)26.[HAlW12O40]][Co(Phen)2(H2O)]2·4H2O (26)27.[PW12O40][Ag4(bzmd)2](27)28.[Ag6(bzmd)2][SiW12O40](28)29.[Cu3(4,4’-bpy)3][PMo12O40]·(C5H6N2)(29)30.[HPW12O40][Cd(2,2’-bpy)3](2,2’-bpy)(30)31.[SiW12O40][Cd(2,2’-bpy)2]2(31)32.[Cu(Phen)2]2[Cu11Cl7(Phen)8][PW12O40])(32)33.{[PMo12V2O42][Cu(enMe)2][Cu(enMe)2(H2O)]}[Cu(enMe)2(H2O)](33)The transition metals, organic ligands and reaction system pH value on theinfluence of the reaction products were studied. On the bases of X-ray structuralanalyses, these compounds have been characterized by elemental analysis, IR, UV-Vis, EPR, fluorescence, X-ray photoelectron spectroscopy (XPS) and XRD. Thethermal analyses, electrochemistry and magnetism properties of some compoundshave been studied, which would take an important role in the explorations ofstructures and functions for the compounds. We will mainly discuss the former25compounds in this thesis.1. vanadium-oxygen clustersApplying in hydrothermal synthesis reactions, we synthesized a vanadium-oxygenclusters (compound1). Compound1is a novel compound based on [V16O39Cl]6-andtransition metal complexes (TMCs)[Fe(Phen)3]2+.[V16O39Cl]6-is the firstpolyoxoanion constructed from15VO5square pyramids and one VO4tetrahedron, itis novel that the VO4tetrahedron in the anion has two terminal oxygen atoms.Detailed analysis reveals that there exist a large number of strong O-H···O and C-H···O hydrogen bonding interactions in compound1. Through the hydrogen bondinginteractions a novel3-D supramolecular network structure is formed. The X-raysingle crystal analyses, elemental analysis, IR, XPS, UV-Vis and XRD have beenperformed on compound1. In addition, variable-temperature magnetic susceptibilitymeasurements of compound1reveals the feature of antiferromagnetic exchange.2. Molybdenum-oxygen clustersApplying in hydrothermal synthesis reactions, we synthesized two molybdenum-oxygen clusters (compound2-4). There contains two kinds of different1-D supramolecular chain structures in compound2. It is interesting that the two differentchains are interwoven into a novel2-D layer structure. Further analysis of compound2reveals that there also contains very complex C-H···O hydrogen bondinginteractions. These hydrogen bonds increased the stability of the crystal of2andconnect the POMs, organic ligands and water molecules into a3-D supramolecularstructure. A novel1-D chain structure is constructed from polyoxoanions, metal ionsand organic ligands connected together with POM-M-L-M-POM linking fashion incompound3. The X-ray single crystal analyses, elemental analysis, IR, XPS, UV-Vis,TG and XRD have been performed on compounds2-3. In addition, The fluorescenceand electrochemistry performance of compound3have been investigated.3. Tungsten-oxygen clustersApplying in hydrothermal synthesis reactions, we synthesized5Tungsten-oxygenclusters (compound4-8). Compounds4-6are examples of compounds based onorganic ligands and POMs. Through the hydrogen bonding interactions, compound4exhibits a supramolecular2-D layer structure, compound5exhibits a novelsupramolecular double chain structure, compound6contains a1-D chain structurewith two2,2’-bpy ligands as double bridges. Two novel POMMOFs are constructedfrom polyoxoanions, metal ions and organic ligands connected together with POM-M-L-M-POM linking fashion in compounds7-8. Compound7exhibits a novel3-Dframework structure, while compound8exhibits an unprecedented2-D layeredframework structure in that their TMCs are constructed from two different organicligands. These compounds have been characterized by X-ray single crystal analyses,elemental analysis, IR, XPS, TG, fluorescence, UV-Vis and XRD. In addition, Theelectrochemistry properties of compounds7-8have been investigated.4. bis-capped Keggin metal-oxygen clustersApplying in hydrothermal synthesis reactions, we synthesized9bis-capped Kegginmetal-oxygen clusters (compound9-17). Compound9represents example of bis-vanadium-capped Keggin molybdenum-vanadium polyoxoanion tri-supported mixed-valent transition metal coordination complex via both terminal-and bridge-oxygenatoms. Compounds10-12represent examples of1-D supramolecular chain structuresthrough the hydrogen bonding interactions based on {PMo12Sb2O40} and differentorganic moieties. Compounds13-15are compounds with discrete structuresconstructed from {PMo12Sb2O40} polyoxoanions and different transition-metal coordination fragments. It is interesting that the POMs in compounds13and14arearranged into a novel face centered lattice and a novel body centered lattice,respectively. Compound15is linked through the hydrogen bonding interactions into anovel3-D network structure. The most remarkable feature of16is that the novelanion [PMo12Sb2O40]2-is utilized as a multidentate chelating ligand, coordinating tofour [Cu(Im)2]+TMCs via terminal oxygen atoms and bridging oxygen atoms to yieldan unprecedented1-D chain structure. An unusual feature of17is that it contains anovel metal halide cluster {Cd(Phen)2]2Cl}3+, and the “butterfly” clusters acting asbridges interconnect the [PMo12Sb2O40]3-POMs into a novel chain structure. It is thefirst extended structure constructed from POMs [PMo12Sb2O40]3-, TMCs and halideions synchronously. These compounds have been characterized by X-ray singlecrystal analyses, elemental analysis, IR, XPS, TG, UV-Vis and XRD etc. In addition,variable-temperature magnetic susceptibility measurements of compound9revealsthe feature of antiferromagnetic exchange.5. Compounds based on polyoxometalates and metal halide clustersApplying in hydrothermal synthesis reactions, we synthesized8compounds basedon polyoxometalates and metal halide clusters (compounds18-25). The crystalstructures of compounds18-19are isomorphous and the metal halide clusters incompounds18and19are hepta-nuclear. The crystal structures of compounds20-25are isomorphous too, they represent examples of the novel compounds based onpolyoxometalates and ennea-nuclear metal halide clusters. Furthermore, there existchloride ions in compounds20-22, and the halide ions in compounds18-19and23-25are iodine ions and bromide ions, respectively. These compounds have beencharacterized by X-ray single crystal analyses, elemental analysis, IR, XPS, UV-Visand XRD. In addition, the thermal analyses of the compounds have been investigated.更多还原