两例过渡金属夹心的杂多钨酸盐的合成及结构

发布时间：2018-05-25 02:23

本文选题：夹心型结构多酸 + Keggin型　；参考：《东北师范大学》2016年硕士论文

【摘要】：多酸(POMs)通常是由W,Mo和V组成的金属氧簇。它们在催化和医药领域存在潜在的应用价值,并且具有多种的尺寸以及性能。在这些金属氧簇中的某些金属离子可以被其他的过渡金属所替换,例如过渡金属到多酸中的替换就是一个发展完备的领域。这样的过渡金属取代多酸簇是非常有意思的,因为它们可以作为二级构筑块来构筑扩展结构,例如二聚的夹心型结构,三聚物和四聚物。而且,过渡金属取代多酸簇的设计和合成为多酸簇的系统合成提供了平台,使得这些多酸簇有着新的物理性质,或者能够扩展多酸的应用范围以及提高多酸的氧化还原性质。基于此,本文中我们选择在常温水溶液条件下,分别以{BiW9)和{SiW9}为前驱体,与过渡金属离子Cu~(2+)进行反应,成功地合成出了两例具有特殊夹心型结构的多阴离子簇。化合物1是一例独特的夹心型结构,夹心结构中包含两个钠原子以及四个铜原子,它们以特殊的方式连接成一个环状结构,从而形成一个六夹心型结构。化合物2的结构也很特殊,不同于以往的三夹心型结构,在化合物2的夹心结构中包夹了三个独立扭曲的Cu-O八面体。虽然夹心型结构多酸很常见,但是本文中的两例夹心型多酸在结构上具有新颖性。H_8{(BiW_9O_(33))_2[Cu(H_2O)]_3[Cu(H_2O)_2][Na(H_2O)_2]_2}·7H_20(1)K_(14){(SiW_9O_(34))_2[Cu(H_2O)_2]_3}-9H_2O (2)并通过X-射线单晶衍射、X-射线粉末衍射、IR和TG等手段对这两个化合物的结构及性质进行了表征。此外,在化合物(1)和(2)的晶体结构中,每个夹心型结构都是单个存在的,它们之间没有相互连接成链状,网状或三维立体结构。值得注意的是,虽然在反应过程中选用的过渡金属都是Cu~(2+),但是由于前驱体的不同,造成夹心结构中的金属氧簇的个数和配位方式也有所不同。虽然二者都是夹心型结构,但是在结构上的区别也是显而易见的。
[Abstract]:Polyoxometalate (POMs) is usually a metal oxygen cluster composed of Mo and V. They have potential applications in the field of catalysis and medicine, and have a variety of dimensions and properties. Some metal ions in these oxygen clusters can be replaced by other transition metals such as transition metal to polyacid is a well-developed field. Such transition metal substituted polyacid clusters are interesting because they can be used as secondary building blocks to construct expanded structures such as dimeric sandwich structures trimer and tetramer. Moreover, the design and synthesis of transition metal substituted polyacid clusters provide a platform for the systematic synthesis of polyacid clusters, which make them have new physical properties, or can expand the range of applications of polyacids and improve the redox properties of polyacids. In this paper, we have selected {BiW9) and {SiW9} as precursors to react with transition metal ion (Cu~(2) under the condition of normal temperature aqueous solution, and we have successfully synthesized two polyanions with special sandwich structure. Compound 1 is a unique sandwich structure, which consists of two sodium atoms and four copper atoms, which are connected into a ring structure in a special way to form a six-sandwich structure. The structure of compound 2 is also very special, which is different from the former triple sandwich structure. In the sandwich structure of compound 2, three independent twisted Cu-O octahedrons are embedded in the sandwich structure of compound 2. Although the sandwich structure of polyacids is common, But the two sandwich polyacids in this paper are novel in structure. H8 {BiW9OOO / S _ 3 _ S _ 2 [Cuo H2O2)] 2 [Cu(H_2O)_2] [Na(H_2O)_2] 2 [Cu(H_2O)_2] [Na(H_2O)_2] 2} 7H201C ~ (14). The structure and properties of the two compounds have been characterized by means of X-ray diffraction X-ray diffraction (X- ray diffraction, single crystal diffraction, IR, TG, TG etc.). The structure and properties of the two compounds have been characterized by means of X-ray diffraction, single crystal diffraction, IR, TG and so on. The structure and properties of the two compounds have been characterized by means of X-ray diffraction, X-ray diffraction, single crystal diffraction, IR and TG. The structure and properties of the two compounds have been characterized by means of X-ray diffraction, X-ray diffraction, single crystal diffraction, IR and TG. In addition, in the crystal structures of compounds 1) and 2), each sandwich structure exists in a single form, and they are not connected to each other into chain, reticular or three-dimensional structures. It is worth noting that although the transition metals used in the reaction process are all Cu~(2, the number and coordination mode of the oxygen clusters in the sandwich structure are different due to the difference of the precursors. Although both are sandwich structure, but the structural difference is also obvious.
【学位授予单位】：东北师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641.4

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