摘要
功能性多金属氧簇(也叫多金属氧酸盐，简称POMs)的分子基杂化化合物是近年来多酸化学的一个研究热点，这主要是因为多金属氧酸盐的催化，电子与质子的储存／传递和光致／电致变色性能。多金属氧簇的有机亚胺衍生物，由于多金属氧簇的金属d-轨道与芳香亚胺共轭体系的π轨道互相作用而产生新的电子结构和相应的理化性能。本论文通过分子设计合成各种多金属氧簇有机亚胺衍生物，研究这些新化合物的结构，性能及其之间的关系，探索和开发新的催化剂、导电材料和光电材料等。
本论文对多金属氧簇有机-无机分子基杂化化合物的研究成果进行了全面系统的总结，尤其是对多金属氧簇的有机亚胺衍生物的合成，结构和性能进行了分析，综合和归纳。
本论文在前人研究的基础上，采用DCC脱水法合成了7个新的多金属氧簇分子基杂化化合物—六钼酸盐有机亚胺衍生物，其中包括二个端氧单取代产物，一个对位端氧二取代产物，二个邻位端氧二取代产物，一个邻位端氧混和配体二取代物，和一个邻位端氧-桥氧混和三取代物，并进行了元素分析，IR，UV-Vis，~1H-NMR表征，其中四个产物晶体用X-射线单晶衍射法测定了分子和晶体的结构。这些研究成果进一步丰富了多金属氧酸盐亚胺衍生物化学。
本论文的主要研究成果如下：
1．合成了七个新的多金属氧簇分子基杂化化合物—六钼酸盐有机亚胺衍生物
1) 六钼酸根的邻甲氧基苯胺的邻位端氧二取代产物。此邻位端氧二取代产物属于三斜晶系，空间群为P(?)，晶体中，两个阴离子簇在π-π堆积和氢键共同作用下以二聚体形式存在，这些二聚体之间又通过三种C-H…O氢键形成一条链状超分子结构。
2) 六钼酸根的2，6-二甲基苯胺的邻位端氧二取代衍生物的新晶型-α。
Functional organic-inorganic molecular-based hybrids of metal-oxo clusters (also called polyoxometalates (POMs)) have drawn tremendous attention, in recent years, because of the properties of POMs such as catalysis, storage and transfer of electron and proton, photo/electro -chromism etc. The studies on organoimdo derivatives of POMs in this dissertation are based on POMs as a good electron accepter. More excellent properties of these organoimido derivatives can be adjusted by strong d-π interactions between POM and organic imide ligand, where space occupied by conjugation π electron of the ligand may be extended to the inorganic framework of POM. The aim of this dissertation is to prepare new organoimido derivatives of POMs in the light of the principles of molecule design. The researches on structures, properties and structure-property relationships of the novel compounds will play an important part in explorations and developments of new catalyzers, electric-materials and photoelectric-materials.
This dissertation has systemically summarized studies up to date on the functional organic-inorganic molecular-based hybrids of metal-oxo clusters, especially, the syntheses, structures and applications of organoimido derivatives of POMs.
In this dissertation, seven new organoimido derivatives has been synthesized by DCC dehydration method with various aromatic amine ligands, which are two mono-functionalized derivatives substituted at terminal oxygens, one trans-bifunctionalized derivative at terminal
引文
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