【作者】 史振雨；

【导师】 彭军；

【作者基本信息】 东北师范大学 ， 无机化学， 2006， 硕士

【摘要】 本论文采用预制的Keggin簇为基本构筑单元,利用含氮螯合或桥连配体,借助配位共价键或分子间相互作用来修饰或桥连Keggin簇,进而构筑了九个新型的有机-无机杂化化合物。另外,利用已知的{Mo8O26}簇为建筑块合成了一个一维链状化合物。并对它们通过元素分析,IR,EPR,XPS,TG和单晶X-射线分析对这些晶体的结构进行了表征,探讨了在水热条件下合成前九个化合物的反应规律,并初步探索了影响这类化合物结构的因素。1.利用Keggin簇为建筑单元,通过络合物片段{MxLy}(M =过渡金属, L =螯合配体)对其修饰,合成了七个新型的有机-无机杂化化合物:{[Co(phen)2]2[SiMoVI8MoV4O40(VIVO)2]}·H2O 1{[Co(phen)2]2[PMo12O40(VO)2]}{[Co(phen)2(OH)]2[PMo12O40(VO)2]}·2.5H2O 2[Cu(phen)2]2{[Cu(phen)]2[SiMo12O40(VO)2]} 3{[Zn(phen)2]2[GeMo12O40(VO)2]}{[Zn(phen)2(H2O)]2[GeMo12O40(VO)2]}·3H2O 4[M(2,2?-bpy)2(H2O)]2[SiMoVI8MoV4VIV2O42] (M = Co 5, Zn 6)[Ni(2,2?-bpy)2(H2O)]2[PMoVI7MoV5VIV2O42] 7其中,phen = 1,10-phenanthroline,2,2?-bpy = 2,2?-bipyridine。研究发现:(1)在该体系中,使用氧化还原性不同的Keggin型多金属氧酸盐对最终产物的结构没有影响,这七个化合物的结构都是建立在二帽Keggin簇的基础上;(2)使用具有不同空间占有率的螯合配体,如phen和2,2?-bpy,所得到的化合物的结构有很大的差异。使用phen作为螯合配体合成了化合物1-4:化合物1是一个孤立的二帽Keggin簇,2为二维层状化合物,3和4均为二帽多支撑型化合物。1和2的结构不同跟配体phen的量密切相关,而其它几个的结构差异则跟金属离子的特征密切相关。使用2,2?-bpy作为螯合配体只能得到结构均为二帽二支撑型的同构化合物5-7。2.利用Keggin簇为建筑单元,通过引入桥连配体,合成了两个新型的有机-无机杂化化合物, {Cu3(4,4?-bpy)3(H2O)[PMo12O40(VO)2]·5H2O 8和(H2bpy)4[Si2MoVI16MoV8O80(VIVO)4]·2H2O 9。化合物8是由分子双梯间相互平行贯穿而形成的三维网状结构,化合物9是Keggin簇的二帽二聚体,其中,所有的4,4?-bpy分子均质子化,充当反荷离子。3.利用{Mo8O26}簇为建筑单元,通过同时引入螯合配体2,2?-bpy和桥连配体phnz ,合成了一个一维链状的具有绿色荧光活性的杂化化合物,(H3O)[Ag3(2,2?-bpy)2(phnz)2(β-Mo8O26)] ( phnz = phenazine) 10。更多还原

【Abstract】 In this paper, nine new organic-inorganic hybrid compounds based on pre-preparedKeggin clusters have been synthesized by utilizing various organic chelating or bridgingN-donor ligands. In addition, by using {Mo8O26} as building block, a new 1D chainlikecompound has been prepared. All these compounds have been structurally characterizedby elemental analyses, IR, EPR, XPS, TG and X-ray single crystal diffractions. The rolesof the first nine compounds under hydrothermal conditions and the factors influencing thestructures of these compounds have also been studied.1. Seven new organic-inorganic hybrid compounds have been prepared by usingKeggin clusters as building blocks and introducing complex fragments{MxLy} (M =transition metal ions, L = chelating ligands):{[Co(phen)2]2[SiMoVI8MoV4O40(VIVO)2]}·H2O 1{[Co(phen)2]2[PMo12O40(VO)2]}{[Co(phen)2(OH)]2[PMo12O40(VO)2]}·2.5H2O 2[Cu(phen)2]2{[Cu(phen)]2[SiMo12O40(VO)2]} 3{[Zn(phen)2]2[GeMo12O40(VO)2]}{[Zn(phen)2(H2O)]2[GeMo12O40(VO)2]}·3H2O 4[M(2,2?-bpy)2(H2O)]2[SiMoVI8MoV4VIV2O42] (M = Co 5, Zn 6)[Ni(2,2?-bpy)2(H2O)]2[PMoVI7MoV5VIV2O42] 7 (phen = 1,10-phenanthroline,2,2?-bpy= 2,2?-bipyridine). From these compounds, we can conclude:(1) in such system, Keggin-type polyoxometalates with different redox propertieshave no obvious structural influences on these compounds. The structures of thesecompounds are all based on bicapped Keggin clusters.(2) The structures of these compounds are significantly different when chelatingligands with different steric possession, such as phen and 2,2?-bpy, are used. Using phen,compounds 1-4 are prepared: compound 1 is a discrete bicapped Keggin cluster,compound 2 is a 2D layer, while 3 and 4 are both bicapped multisupporting Kegginclusters. The structural difference between 1 and 2 is owing to tha amount of phen, whilethe structural differences among other compounds are ascribed to the characteristic ofmetal ions. Using 2,2?-bpy, we can only obtain three isostructural bicapped bisupportingKeggin clusters 5-7.2. Two novel organic-inorganic hybrid compounds have been synthesized by usingKeggin cluster as building blocks and 4,4?-bpy as bridging ligand:{Cu3(4,4?-bpy)3(H2O)[PMo12O40(VO)2]·5H2O 8(H2bpy)4[Si2MoVI16MoV8O80(VIVO)4]·2H2O 9Compound 8 is a 3D interpenetrating network formed by parallel interpenetration of 1Ddouble ladders. Compound 9 is a bicapped Keggin dimerized polyanion, and all4,4?-bipyridine molecules in compound 9 are completely protonated and function ascountercations.3. A novel chainlike hybrid with green fluorescent emission has been synthesized byusing {Mo8O26} as building block and introducing the chelating ligand 2,2?-bpy andbridging ligand phnz: (H3O)[Ag3(2,2?-bpy)2(phnz)2(β-Mo8O26)] (phnz = phenazine) 10.更多还原