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基于B型仲钨酸盐和Anderson型多金属氧酸盐的功能化无机—有机杂化化合物的研究

The Study of the Functionalized Inorganic-Organic Hybrid Compounds Based on B-type Paradodecatungstates and Anderson-type Polyoxometalates

【作者】 钟艳

【导师】 王恩波;

【作者基本信息】 东北师范大学 , 无机化学, 2010, 硕士

【摘要】 本论文利用常见的多金属氧酸盐簇为基本建筑单元,以过渡金属为桥连剂,构筑出新型的多金属氧酸盐无机-有机杂化化合物,探究这类物质的独特性质及潜在应用价值。我们利用常规合成方法合成了4个新型的多金属氧酸盐化合物,通过元素分析,X-射线单晶衍射,IR和TG对晶体结构进行了表征。1.以[H2W12O42]10-为基本建筑块,得到了2个新的无机-有机杂化化合物: Na6[{Cu(gly)(H2O)}]2[{Cu(H2O)}(H2W12O42)]·21H2O (1) Na{Na(H2O)6}{Na(H2O)4}3[{Cu(gly)2}]2{H5(H2W12O42)}·8.5H2O (gly = glycin) (2)在化合物1中,[H2W12O42] 10-建筑单元通过[Cu(H2O)]2+基团和[Cu(gly)(H2O)]+连接形成二维层状结构,然后进一步通过Na原子连接成三维网状结构。在化合物2里,被2个[Cu(gly)2]基团修饰的[H2W12O42] 10-通过六个Na原子连接形成二维层状结构。2.以Anderson结构多金属氧酸盐簇为基本建筑单元,通过铜-甘氨酸配合物修饰或桥连得到了1个新的多金属氧酸盐化合物: Na[(Gly)2Cu][Cu(H2O)4Cr(OH)6Mo6O18]·6H2O (3)化合物3显示了二维窗格型的网络结构。3.以B型仲钨酸盐簇为基本建筑单元,过渡金属锰桥连合成1个新型一维链状化合物: [Na6(H2O)18][Mn2(H2O)6(H2W12O42)]·6H2O (4)化合物4是由1D链[Mn2(H2O)6(H2W12O42)]n6-和[Na6(H2O)18]n6+连接成的二维层结构。另外,我们还探讨了化合物1和2的光催化性质。实验结果表明,这两个化合物在光降解罗丹明B时是很好的光催化剂。

【Abstract】 The aim of this paper is the synthesis of new polyoxometalate compounds on the basis of familiar polyoxoanion clusters and transition metal ions. The study on unique characteristics and potential applications for these new compounds are also carried out. Four new polyoxom- etalate compounds have been synthesized and structurally characterized by elemental analyses, single X-ray crystal diffractions, IR and TG analyses.1. On the basis of [H2W12O42]10-, two new inorganic- organic hybrid compounds have been synthesized and structurally characterized: Na6[{Cu(gly)(H2O)}]2[{Cu(H2O)}(H2W12O42)]·21H2O (1) Na{Na(H2O)6}{Na(H2O)4}3[{Cu(gly)2}]2{H5(H2W12O42)}·8.5H2O (gly = glycin) (2) In compound 1, [H2W12O42]10- building block connects two neighboring clusters with [Cu(H2O)]2+ groups and [Cu(gly)(H2O)]+ groups to form a two-dimensional (2D) layer struct- ure, which are further joined together by Na atoms to form a three-dimensional (3D) network. In compound 2, the [H2W12O42]10- cluster that is decorated by two [Cu(gly)2] moieties conne- cts four adjacent clusters with six Na atoms into a two-dimensional (2D) layer.2. We have synthesized and structurally characterized one new polyoxometalate compo- und on the basis of Anderson type polyoxoanion cluster and Cu-Gly complexes: Na[(Gly)2Cu][Cu(H2O)4Cr(OH)6Mo6O18]·6H2O (3) Compound 3 exhibits an 2D window-like network.3. On the basis of transition metal manganese and paradodecatungstates, one new com- pound have been synthesized and structurally characterized: [Na6(H2O)18][Mn2(H2O)6(H2W12O42)]·6H2O (4) Compound 4 consists of an unusual 2D layer which is formed by the interconnection of 1D [Mn2(H2O)6(H2W12O42)]n6-and [Na6(H2O)18]n6+ chains.In addition,photocatalysis properties of compounds 1 and 2 have also been investigated. The experiments prove that these two compounds are good photocatalysts for photocatalytic degradation of Rhodamine B.

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