节点文献
钼（钒）金属—氧簇的合成、结构与性能
Syntheses, Structures and Properties of Molybdenum (Vanadium) Metal-oxygen Clusters
【作者】 石淑云；
【作者基本信息】 吉林大学 ， 无机化学， 2010， 博士
【摘要】 本论文是在水热合成条件下,使用成簇元素（Mo,W,V,等）的酸（盐）或是氧化物,引入适当的还原剂、选择合适的有机配体及第二种过渡金属,控制温度与pH等条件,合成了一系列具有新颖结构、优异性能的新型氧簇。所有合成的化合物都进行了元素分析,红外光谱及单晶衍射研究,同时对部分化合物的UV-Vis, XPS, TG, XRD, EPR及磁性进行了研究。本论文合成了共十七个金属氧簇化合物,而且都为首次合成。一.合成四个钒（钼）-氧簇合物[Fe（2,2`-bipy）3]2[HV6VV10IVO38（Cl）]·4.67H2O 1; [Ni（enMe）3]2[H4V5VV10IVO36（Cl）]·2H2O 2 ; [HN（C2H5）3]3[PMo12O40]3 ;[NH2（C2H4NH2）2][Mo5P2O23] 4。1是由簇[HV6VV10IVO38（Cl）]6-与过渡金属配离子[Fe（2,2′-bipy）3]3+形成的二维超分子化合物; 2是由簇核[H4V5VV10IVO36（Cl）]4-与平衡阳离子[Ni（enMe）3]2+结合形成新颖的二维超分子化合物。3是pseudo-Keggin结构阴离子[PMo12O40]3-和质子化的阳离子TEA通过多点氢键形成三维超分子网络结构。4是[Mo5P2O23]6-阴离子和一个质子化的DETA阳离子通过多点氢键形成有趣的三维超分子网络结构。二.合成了两个As-V-O簇合物[HAs6V15O42（H2O）][Cu（enMe）2]2.5·2H2O 5;[H2enMe]2 [As8V14O42 （H2O）]·3H2O 6。5独特之处在于簇阴离子和两个不同构型双桥阳离子按照A-B-C-B-A-B-C-连接方式形成新颖一维链,链与链之间靠砖墙式的堆积方式形成二维空间结构。6含有特殊堆积方式的簇阴离子,三个相邻的簇阴离子聚合在一起形成一个等边三角形结构,这个聚合单元沿着c轴形成-A-B-A-B-堆积模式。三.合成了七个具有Keggin结构的Mo-V-O簇合物[PMo8V6O42][Co（Phen）2（H2O）]2[TEA]2·H3O·3H2O 7; [PMo8V6O42][Ni（Phen）2 （H2O）]2[TEA]2·H3O·3H2O 8; [PMo8V6O42][Zn（Phen）2]2[4,4′-bpy]·H3O·3H2O 9; [PMo8V6O42][Co（Phen）2][py]·4H2O 10 ; [PMo8V6O42][Co（Phen）2] [Him]2·2H3O·3H2O 11; {[PMoVI10VIV4O42][Co（Phen）2（H2O）]2}{[PMoVI10VIV4O42] [Co（Phen）2]2}·2OH-·4,4′-bpy 12; [H2NC4H8NH2]6 [MoVI16VV12P2O84]·4H2O 13。7-11的共同点是簇合物中有簇阴离子[PMo8V6O42]6-,过渡金属阳离子,不同的有机胺以及水分子。化合物7,8和9都是簇阴离子支撑着过渡金属阳离子,形core {PMo12O40} with two antimony atoms capping two opposite pits. The most remarkable feature of compound 14-16 are that the novel anion [PMo12O40Sb2]2- is utilized as a multidentate chelating ligand, coordinating to the transition metal complex via the terminal oxygen atoms to yield an unprecedented 1-D chain. The linking mode of the chain is -A-A-A among compounds 14-16. For compound 17, it contains the first two types of Sb capped Keggin anions. The Si1, Si2 and Si3 POMs are connected together into a 2-D supramolecular layer （layer A） structure through the O···O interactions of the terminal oxygen atoms of the adjacent Si1, Si2 and Si2 POMs. The linking mode of the layer based on Si1 and Si2 POMs is -A-B-A-, while the linking mode of the layer based on Si3 is -A-A-A-. The most interesting feature is that the two different type layers are stacked together alternately. There still exit very complex hydrogen bonding interactions between the oxygen atoms of the anions and the water molecules into a novel supramolecular structure.
【Abstract】 In this paper, by the applications of hydrothermal technique, through the use of a metal element （Mo, W, V etc.） acid （salt） or oxides, selecting the appropriate organic ligands as well as the second transition metal salts, controlling the temperature and pH of reaction system, we synthesized a series of polyoxometalates with novel structures and interesting properties. The structures of all the compounds have been characterized by elemental analyses, IR spectra and X-ray diffraction analyses, some compounds have been characterized by UV-Vis, XPS spectra, TG, XRD, EPRanalyses and magnetic property studies.In this paper, 17 new metal oxygen clusters were synthesized.I. Vanadium oxygen clusters and molybdenum- oxygen clusters By the applycation of hydrothermal synthesis technology, we synthesized two vanadium oxygen clusters and two molybdenum oxygen clusters. [Fe（2,2`-bipy）3]2[HV6VV10IVO38（Cl）]·4.67H2O 1; [Ni（enMe）3]2[H4V5VV10IVO36 （Cl）]·2H2O 2; [HN（C2H5）3]3[PMo12O40] 3; [NH2（C2H4NH2）2][Mo5P2O23]4. Compound 1 is composed of the [HV6VV10IVO38（Cl）]6- and transition metal complex [Fe（2,2`-bipy）3]3+, Compound 2 is composed of an [H4V5VV10IVO36（Cl）]4- cluster and [Ni（enMe）3]2+. Both compounds are further linked into a novel two dimensional structure through hydrogen bonds. Compound 3 is composed of a pseudo-Keggin [PMo12O(40]3- anions and the protonated TEA cations. Compound 4 is composed of the [Mo5P2O23]6- anions and the protonated DETA moieties. Compound 3 and Compound 4 all exhibit an unusual 3-D supramolecular network structure through N-H···O hydrogen bonding interactions.II. AsIII-VIV Polyoxometalates oxygen clustersBy the applycation of hydrothermal synthesis technology, we synthesized two AsIII-VIV polyoxometalates. [HAs6V15O42（H2O）][Cu（enMe）2]2.5·2H2O 5;[H2enMe]2 [As8V14O42 （H2O）]·3H2O 6. The two compounds have been firstly hydrothermally synthesized. X-ray crystallographic studies reveal that compound 5 represents the first example of 2-D structure constructed from [HAs6V15O42（H2O）]5- anions and TMCs. The anions [HAs6V15O42（H2O）]5- are connected by two different types of double-bridges into a novel chain structure. Moreover, there exits the“orientation”of the anions in chains, it exhibits an unprecedented -A-B↑-C-B↓-A-B↑-C-B↓- linking mode. And the chains are further connected into a brick-wall-like two-dimensional layer structure constructed from POMs and TMCs. Compound 6 exhibits very interesting stacking mode. The trimers are stacked along the c axis into a novel -A-B-A-B- stacking mode.III. Keggin-structure molybdenum-vanadium oxygen clustersBy the applycation of hydrothermal synthesis technology, we synthesized seven Keggin-structure tungsten oxygen clusters. [PMo8V6O42][Co（Phen）2（H2O）]2 [TEA]2A·H3O·3H2O 7; [PMo8V6O42][Ni（Phen）2（H2O）]2[TEA]2·H3O·3H2O 8; [PMo8V6O42][Zn（Phen）2]2[4,4′-bpy]·H3O·3H2O9; [PMo8V6O42][Co（Phen）2][py]·4H2O 10; [PMo8V6O42][Co（Phen）2][Him]2·2H3O·3H2O 11; {[PMoVI10VIV4O42][Co（Phen）2 （H2O）]2}{[PMoVI10VIV4O42][Co（Phen）2]2}·2OH-·4,4′-bpy 12; [H2NC4H8NH2]6 [ MoVI16VV12 P2O84]·4H2O 13The seven compounds all were first synthesized. Compounds 7-11 all contain [PMo8V6O42]5- anion, transition metal complex, organic amine, protonated water molecule, and water molecules. Compound 7, 8 and 9 are POM supported coordination complexes, while the compound 10 and compound 11 exhibit 1-D extended structures. In addition, the POMs, TMCs and the organic amines construct a supramolecular structure through hydrogen bonds between the oxygen atoms of the water molecules and the oxygen atoms of the anions and the weak van der Waals interactions. Among compounds 10, 11 and 12, there exit a mass of phenol rings between organic amine and transition metal complex, however, there did not exist strongπ···πinteractions between the rings for the steric hindrance.Compound 12 contains two half of crystallographically different anions [PMoVI10VIV4O42]3-, named as POM 1 and POM 2, respectively. The POM 1 supports two [Co（Phen）2（H2O）]2+ TMCs with the Co-O bond forming a novel bi-supported coordination complex. POM 2 interconnect [Co（Phen）2]2+ via the Co-O bonds to yield an unusual infinite 2-D {[PMo10V4O42][Co（Phen）2]2+} positive layer. Moreover, the discrete POM is sandwiched by two adjacent layers into a novel–ABAB- stacking fashion. According to the synthesis of Compound 7-12, we can get an interesting conclusion: different building blocks will build different structures. This approach using different building blocks to build different structures is quite attractive and appears to hold the key to the development of rational approaches for tailor-making materials based on polyoxometalates with desirable features. Compound 13 is composed of [MoVI16VV12P2O84]14- by polymerization of two basic unit { Mo8V6P O42}, containing six piperazines and five water molecules around. The every four dimers and the seven piperazines along a certain direction are formed wind model like units through the hydrogen bonds, and the sub-unit repeats expansion to form a beautiful two-dimensional polymer layer, and then stacks into a three-dimensional network structure.V. Keggin-structure molybdenum- antimony oxygen clustersBy the applycation of hydrothermal synthesis technology, we synthesized four Keggin-structure molybdenum- antimony oxygen clusters. [PMo12Sb2O40][Cu （enMe）2]·4H2O14;[PMo12Sb2O40][Ni（enMe）2]·4H2O15;[PMo12Sb2O40][Cu（en）2]·H3O·H2O 16; [SiMoVI9MoV3O40Sb2][SiMoVI7MoV5O40Sb2]（H2en）2 （en）0.5·（H2O）8 17.Since our group prepared the first Sb capped Pseudo-Keggin POM {PMo12O40Sb2} in 2006, Compounds 14-17 were prepared first time for extended structures containing antimony. Compounds 14-16 all exhibit the well-known Pseudo-Keggin core {PMo12O40} with two antimony atoms capping two opposite pits. The most remarkable feature of compound 14-16 are that the novel anion [PMo12O40Sb2]2- is utilized as a multidentate chelating ligand, coordinating to the transition metal complex via the terminal oxygen atoms to yield an unprecedented 1-D chain. The linking mode of the chain is -A-A-A among compounds 14-16. For compound 17, it contains the first two types of Sb capped Keggin anions. The Si1, Si2 and Si3 POMs are connected together into a 2-D supramolecular layer （layer A） structure through the O···O interactions of the terminal oxygen atoms of the adjacent Si1, Si2 and Si2 POMs. The linking mode of the layer based on Si1 and Si2 POMs is -A-B-A-, while the linking mode of the layer based on Si3 is -A-A-A-. The most interesting feature is that the two different type layers are stacked together alternately. There still exit very complex hydrogen bonding interactions between the oxygen atoms of the anions and the water molecules into a novel supramolecular structure.
【Key words】 hydrothermal synthesis； polyoxometalates oxygen cluster； crystal structures； supramolecular； magnetic property；