本文關(guān)鍵詞： 多金屬氧簇 Anderson-Evans 有機共價修飾 triol配體　出處：《吉林大學(xué)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：多金屬氧簇是由氧橋聯(lián)前過渡金屬形成的多核簇合物,在光化學(xué),催化,磁性及醫(yī)藥領(lǐng)域均有廣泛的應(yīng)用。為豐富多金屬氧簇的化學(xué)結(jié)構(gòu),拓展簇的功能化應(yīng)用,便需要對多金屬氧簇進行有機修飾,從而獲得多金屬氧簇有機-無機雜化復(fù)合物。在本論文中,我們將主要研究多金屬氧簇的有機共價修飾。以盤狀的Anderson-Evans型多金屬氧簇作為研究對象,其中心雜原子周圍的六個羥基可以全部或部分的被三羥基配體取代,形成有機-無機雜化物。這種方法具有合成簡便,易于連接功能基團,產(chǎn)率高等優(yōu)點,因而被廣泛采用。但是對于此類反應(yīng)中,三羥基配體修飾的類型、影響因素及反應(yīng)機理等方面的研究還比較少。我們以此作為出發(fā)點,開展了以下幾個方面的研究工作:(1)選擇二價銅為中心雜原子,首次制備得到了三羥基配體修飾Anderson-Evans型多金屬氧簇的雙邊半錯位結(jié)構(gòu),同時通過控制溶液的酸堿環(huán)境,實現(xiàn)了不同結(jié)構(gòu)類型之間的轉(zhuǎn)變;(2)利用具有可變價態(tài)的鈷為中心原子,得到了四種三羥基配體修飾Anderson-Evans型多金屬氧簇的結(jié)構(gòu)類型,發(fā)現(xiàn)了在空氣中二價鈷到三價鈷的原位氧化及其伴隨著修飾類型的改變,進一步的研究表明,通過控制反應(yīng)條件,氧化過程可以加速,也可以被抑制。(3)通過控制加入反應(yīng)物的比例,成功制備了一系列三羥基配體修飾的Anderson-Evans型簇反應(yīng)中間體{M2Mo6}(M=Cu2+、Co2+、Ni2+和Zn2+)型化合物。中間體繼續(xù)加入鉬源即可將其轉(zhuǎn)化為相應(yīng)的Anderson-Evans型多金屬氧簇。以含有二價銅的化合物為例,詳細研究了不同環(huán)境條件對修飾類型的影響。通過對三羥基配體修飾的銅和鈷中心Anderson-Evans型多金屬氧簇的研究,成功獲得了新穎的雙邊半錯位修飾的簇結(jié)構(gòu),發(fā)現(xiàn)了酸堿環(huán)境對修飾類型的影響,實現(xiàn)了多種有機配體在多金屬氧簇上的共修飾,并通過控制反應(yīng)條件成功制備了一類可能的反應(yīng)中間體。本論文的研究工作為Anderson-Evans型多金屬氧簇的修飾提供大量的實例,所獲得的理論知識對后續(xù)簇的修飾結(jié)構(gòu)的研究具有一定的指導(dǎo)意義。
[Abstract]:Polyoxometallic clusters are polynuclear clusters formed by transition metals before oxygen bridging. They are widely used in photochemistry, catalysis, magnetism and medicine. They are rich in the chemical structure of polyoxometallic clusters. To expand the functional application of the cluster, it is necessary to modify the polymetallic oxygen cluster organically, so as to obtain the organic-inorganic hybrid complex of the polyoxometallic cluster. We will mainly study the organic covalent modification of polyoxometallic clusters, and take the discoid Anderson-Evans polyoxometallic clusters as the object of study. The six hydroxyl groups around the central heteroatom can be completely or partially replaced by trihydroxyl ligands to form organic-inorganic hybrids. This method has the advantages of simple synthesis, easy connection of functional groups and high yield. Therefore, it is widely used. However, there are few studies on the type of trihydroxyl ligand modification, influencing factors and reaction mechanism in this kind of reaction. We take this as our starting point. The following research work has been carried out: 1) selecting divalent copper as the central heteratomic atom. Trihydroxyl ligand modified Anderson-Evans polyoxometallic clusters were prepared for the first time, and the two-sided semi-dislocation structure was obtained by controlling the acid-base environment of the solution. The transformation between different structure types is realized. Using cobalt with variable valence as the central atom, four kinds of trihydroxyl ligand modified Anderson-Evans polyoxometallic clusters were obtained. The in-situ oxidation of cobalt divalent to trivalent cobalt in air and the change of modification type have been found. Further studies show that the oxidation process can be accelerated by controlling the reaction conditions. It can also be inhibited by controlling the proportion of reactants added. A series of trihydroxy-ligand modified intermediate {M _ 2Mo _ 6} M _ 2Mo _ 2 / Co _ 2 for Anderson-Evans cluster reaction have been successfully prepared. Ni2 and Zn2) compounds. The intermediates can be transformed into corresponding Anderson-Evans polyoxometallic clusters by adding molybdenum source. Take the compound containing divalent copper as an example. The effects of different environmental conditions on the modification types were studied in detail. The Anderson-Evans polyoxometallic clusters of copper and cobalt centers modified by trihydroxyl ligands were studied. A novel two-sided semi-dislocation modified cluster structure was successfully obtained, and the effect of acid-base environment on the modification type was found, and the comodification of various organic ligands on polymetallic oxygen clusters was realized. A class of possible reaction intermediates were successfully prepared by controlling the reaction conditions. This paper provides a large number of examples for the modification of Anderson-Evans polyoxometallic clusters. The theoretical knowledge obtained has certain guiding significance for the study of the modification structure of subsequent clusters.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O641.4

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1 王楊;Anderson-Evans型多金屬氧簇的有機修飾及構(gòu)型轉(zhuǎn)化研究[D];吉林大學(xué);2017年

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本文編號：1480591