【作者】 陈文彬；

【导师】 申少华； 朱莉；

【作者基本信息】 湖南科技大学 ， 应用化学， 2008， 硕士

【摘要】 多金属氧酸盐(polyoxometalates,简写为POMs),通常称为多酸(盐),是由前过渡金属离子通过氧连接而形成的金属-氧簇类化合物。由于多酸具有储存电子、质子的性能,是一类优秀的受体分子,可以与无机分子、有机分子(包括大环化合物)、离子等结合形成超分子化合物。多金属氧簇的有机亚胺衍生物,由于多会属氧簇的金属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。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。本人在前人研究的基础上,采用DCC脱水法详细研究适合于多酸衍生物的合成化学,采用氨基酚系列化合物为配体,对Lindqvist结构类型的含钼多酸根及其衍生物进行化学修饰,并进而利用酯化反应对其作进一步的化学修饰,从而实现钼酸根有机亚胺衍生物分子的功能团化。因此,通过本论文的研究,可以拓展多酸衍生物的制备途径,了解和发现该类有机-无机杂化材料新奇的结构和特异的性能,并为该类化合物在实际工作中的应用提供一定的指导。本人合成了三种新的六钼酸盐有机亚胺衍生物,并测定了对氨基酚双取代衍生物的晶体结构,还通过酯化反应对邻氨基酚单取代衍生物作进一步官能团化。同时发现六钼酸盐的同质多晶现象并测定了其结构。对新合成的六钼酸盐有机亚胺衍生物进行了元素分析、IR、及UV-Vis研究,并选择性地对部分化合物进行了~1H NMR和X-射线单晶结构解析的表征,并探讨了这类化合物的DCC脱水法反应条件,寻求最佳反应条件。更多还原

【Abstract】 The previous transition metal ions combining with oxide are able to form molecular metal-oxide cluster anions,commonly referred to as polyoxometalates or polyoxoanions（POMs）.They are good receptor molecules because of the properties of POMs such as the storage of clectrou and proton,the supramolecular compounds can be combined with inorganic elements,organic molecules（including macrocyclic compounds）and ion.More excellent properties of these organoimido derivatives can be adjusted by strong d-πinteractions between POM and organic imide ligand.where space occupied by conjugationπelectron of the ligand may be extended to the inorganic framework of POM.The aim of 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.In this dissertation,on the basis of previous studies,using DCC dehydration method suitable for more study of the synthesis of acid derivatives,compounds used for paracetamol series ligand,Lindqvist type structure containing molybdenum more radical and chemically modified derivatives,and its use of esterification for further chemical modification. thus achieving molybdenum imine derivatives organic radical elements of the functional groups.Therefore,the dissertation research,can expand acid derivatives preparation,understanding the structure and specific pcrformance of such organic-inorganic hybrid materials,this makes it important for the guidance of the compounds in the actual work.In this dissertation,three new organoimido derivatives has been synthesized by DCC dehydration method.and（n-Bu₄N）₂[Mo₆O₁₈≡（NAr）₂] （Ar=p-C₆H₄OH）has been structurally characterized by X-ray single crystal diffraction.Through the esterification of（n-Bu₄N）₂[Mo₆O₁₈≡NAr] （Ar=o-C₆H₄OH）for further function.Polymorphism has been discovered in organoimido and characterized their structure.All the new complexes were characterized by Elemental analysis,IR,and UV-Vis.Some of the complexes were also characterized by ¹H NMR and thermogravi- metric analysis.The researches on synthesis reactions for these hybrid compounds have been done,in order to look for the optimal conditions.更多还原