本文選題：夾心型結(jié)構(gòu)多酸 + Keggin型�。� 參考：《東北師范大學(xué)》2016年碩士論文

【摘要】：多酸(POMs)通常是由W,Mo和V組成的金屬氧簇。它們在催化和醫(yī)藥領(lǐng)域存在潛在的應(yīng)用價(jià)值,并且具有多種的尺寸以及性能。在這些金屬氧簇中的某些金屬離子可以被其他的過渡金屬所替換,例如過渡金屬到多酸中的替換就是一個(gè)發(fā)展完備的領(lǐng)域。這樣的過渡金屬取代多酸簇是非常有意思的,因?yàn)樗鼈兛梢宰鳛槎墭?gòu)筑塊來構(gòu)筑擴(kuò)展結(jié)構(gòu),例如二聚的夾心型結(jié)構(gòu),三聚物和四聚物。而且,過渡金屬取代多酸簇的設(shè)計(jì)和合成為多酸簇的系統(tǒng)合成提供了平臺,使得這些多酸簇有著新的物理性質(zhì),或者能夠擴(kuò)展多酸的應(yīng)用范圍以及提高多酸的氧化還原性質(zhì)。基于此,本文中我們選擇在常溫水溶液條件下,分別以{BiW9)和{SiW9}為前驅(qū)體,與過渡金屬離子Cu~(2+)進(jìn)行反應(yīng),成功地合成出了兩例具有特殊夾心型結(jié)構(gòu)的多陰離子簇�；衔�1是一例獨(dú)特的夾心型結(jié)構(gòu),夾心結(jié)構(gòu)中包含兩個(gè)鈉原子以及四個(gè)銅原子,它們以特殊的方式連接成一個(gè)環(huán)狀結(jié)構(gòu),從而形成一個(gè)六夾心型結(jié)構(gòu)�；衔�2的結(jié)構(gòu)也很特殊,不同于以往的三夾心型結(jié)構(gòu),在化合物2的夾心結(jié)構(gòu)中包夾了三個(gè)獨(dú)立扭曲的Cu-O八面體。雖然夾心型結(jié)構(gòu)多酸很常見,但是本文中的兩例夾心型多酸在結(jié)構(gòu)上具有新穎性。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)并通過X-射線單晶衍射、X-射線粉末衍射、IR和TG等手段對這兩個(gè)化合物的結(jié)構(gòu)及性質(zhì)進(jìn)行了表征。此外,在化合物(1)和(2)的晶體結(jié)構(gòu)中,每個(gè)夾心型結(jié)構(gòu)都是單個(gè)存在的,它們之間沒有相互連接成鏈狀,網(wǎng)狀或三維立體結(jié)構(gòu)。值得注意的是,雖然在反應(yīng)過程中選用的過渡金屬都是Cu~(2+),但是由于前驅(qū)體的不同,造成夾心結(jié)構(gòu)中的金屬氧簇的個(gè)數(shù)和配位方式也有所不同。雖然二者都是夾心型結(jié)構(gòu),但是在結(jié)構(gòu)上的區(qū)別也是顯而易見的。
[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.
【學(xué)位授予單位】：東北師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O641.4

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