论文部分内容阅读
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.