【作者】 李凯；

【导师】 杨智；

【作者基本信息】 北京理工大学 ， 化学工程与技术， 2014， 硕士

【摘要】 探索新型结构配合物的合成，研究其理化性质和应用，一直是配位化学的中心课题。环状配合物已经成为配合物中很重要的一类化合物。稳定的环状配合物可以通过设计和选择合适的配体与中心原子以及控制反应条件来加以合成得到。含N、O配体结构类似，配位形式多样，且易于制备，因而在配位化学中有重要的应用，且此类配体支持的金属有机化合物的研究成为现代主族化学研究最广泛的领域之一。本论文以Schiff碱配体和氨基桥联的双酚配体为前驱体，合成出4种含N、O配体支持的环状配合物，并获得了化合物的X-射线单晶衍射晶体结构。应用核磁共振、红外光谱、元素分析、热重分析、紫外光谱和荧光光谱等手段对化合物进行了表征和性质研究。选取金属铝为中心原子，研究Schiff碱与含铝化合物形成配合物的晶体结构、稳定性和理化性质。利用三甲基铝与Schiff碱配体反应，合成了一维线性的高分子配合物，与有机高分子相比，晶体状的金属高分子配合物相对来说很少，也很难以合成。三甲基铝作为路易斯酸（电子对受体）与Schiff碱配体反应，形成循环[C–N–Al–(μ-O2)–Al–N–C]n的链的大分子结构，这对于研究金属有机化学在大分子化合物的应用具有重要的理论意义。利用三异丁基铝与Schiff碱反应，形成一个以铝为配位中心的空间对称结构，中心的铝原子呈现五配位排列，这对于分子的稳定具有重要作用。进一步研究了氨基桥联双酚配体在含硅、磷有机化合物合成中的应用，合成并表征了两种新型配合物。氨基桥联双酚配体与二苯基二氯硅烷和三乙胺反应，形成一个十元环的稳定化合物。结构以硅原子为中心呈现立体对称排布，有利于增强结构的稳定。通过热重分析，该结构具有很好的热稳定性，荧光光谱分析表明新型硅化合物具有较强的光致发光性质，可作为潜在的优良有机-无机光敏材料。利用同样的方法与苯基二氯磷反应形成一个以磷为中心的环状稳定化合物。更多还原

【Abstract】 Exploring the syntheses of novel structural complexes, studying their physical andchemical properties as well as their applications is the central motif of coordinationchemistry. Cyclic complexes in coordination compounds have become a very importantclass of compounds. Stable ring complexes can be synthesized by design and selection ofsuitable ligands, central atom and experiment conditions. Ligands containging N, N-or N,O-bidentate have similar structures. The use of these ligands in coordination chemistry hasattracted much attention for several reasons: first, they can be easily synthesized in highyields from readily available starting materials; second, the electronic and steric propertiesof coordination complexes containing N, N-or N, O ligands can be readily tuned byaltering the substituents; third, binding modes to the central atom are virious. The study ofthese complexes is one of the most widely investigated areas of modern main groupchemistry. Four cyclic compounds with N, N-or N, O-bidentate ligands were synthesizedand characterized by single-crystal X-ray diffraction structural analysis,1H NMR, IRspectra, elemental analysis, thermal analysis, UV-vis absorption spectra and fluorescentspectra properties.The synthesis, crystal structure, stability and properties of a series of aluminumcomplexes with Schiff base ligands were studied. The reaction of trimethylaluminum with asalen ligand afforded an one-dimensional structure of an Aluminum coordinationcompound in the crystal state. Comparing with the organic polymer, this type of aluminumcentered macromolecular structure is very rare. Trimethylaluminum as a Lewis acid(electron pair acceptor) reaction with Schiff base ligand, forming the macromolecule withan infinite [C–N–Al–(μ-O-)2–Al–N–C]nchain. It is great significance for the study ofmetal-organic chemical compounds in macromolecular. The reaction of triisobutylaluminium with a salen ligand afforded a structure in the crystal state with pentacoordinatealuminum. X-ray diffraction structures show that compound is a symmetrical structure,which makes the structure framework more stable at the room temperature.With the aim to further investigate the application in silicon and phosphoruscomplexes, two new kind compounds with amine bridged bis(phenol)s ligand weresynthesized and characterized. The reaction of triethylamine with an amine bridgedbis(phenol)s ligand, forming a stable ten-membered ring complexe withdiphenyldichlorosilane. X-ray diffraction structures show that compound is a symmetrical structure with the silicon atom in the center, which makes the structure framework morestable at the room temperature. Compound has good thermal stability through thermalanalyses. The study of fluorescent spectra properties shows that the compound exhibitsstrong fluorescence under ultraviolet light. So they appear to be good candidates for novelpotential organic-inorganic photoactive materials. The reaction of dichlorophenylphosphinewith an amine bridged bis(phenol)s ligand afforded a stable ring complexe structure of anphosphorus coordination compound in the crystal state.更多还原