酰腙类有机分子笼构筑的多孔材料的合成及性质研究

Due to their exclusive solubility in the solvent, porous materials constructed from organic molecular cages own the properties and applications different from ones of other porous materials. Our project plans to synthesize porous materials based on acylhydrazone organic molecular cages. Acylhydrazone groups introduced into the backbones of organic molecular cages will bring many active sites and transform in configurations and isomers. These will give rise to special properties of acylhydrazone organic molecular cages. The syntheses of the acylhydrazone organic molecular cages with different sizes, structures and shapes will be controlled by the concentration of reactants, reaction solvent, temperature and different templates added. Crystals of acylhydrazone organic molecular cages and co-crystals with other organic molecules will grow, the adsorption properties of which will be studied. Their properties of host-guest and luminescence response will be also studied. The organic molecular cages , which adsorb organic molecules with luminescence response as probe molecules, will be deposited on substrates to form film in applications of detection and sensing. Coordination compounds based on acylhydrazone organic molecular cages will be also synthesized. The luminescence and catalysis properties of the coordination compounds will be investigated. This project not noly expand the investigation areas of porous materials constructed from organic molecular cages, but also promote the applications of organic molecular cages. Meanwhile, this project will investigate deeply relationships among the syntheses, structures and properties and lay foundation for the syntheses of porous materials constructed from organic molecular cages with special structures.

有机分子笼特有的溶解性使其构筑的多孔材料具有与其他多孔材料不同的性质和应用。本课题拟合成酰腙类有机分子笼构筑的多孔材料。酰腙官能团引入笼骨架可以给其带来若干的活性位点，同时其还存在着构型互变和异构互变。这些特点将会赋予酰腙类有机分子笼新颖的性质。通过控制反应物浓度、反应溶剂、温度和添加不同的模板剂来控制合成酰腙类有机分子笼的尺寸，结构和形状。合成有机分子笼多孔晶体材料或与其他有机分子的共晶，研究其吸附性能及其在主客体化学和荧光响应方面的性质。选取探针分子吸附在有机分子笼中，并沉积在基质中制备成膜用于检测和传感。合成酰腙有机分子笼的金属配合物，研究其配合物的荧光性质和催化性质。本项研究不仅拓展了有机分子笼构筑的多孔材料的研究领域，而且推进了有机分子笼的应用范围，并将深入研究此类多孔材料的合成、结构及性能之间的关系，为定向合成具有特殊结构与性能的有机分子笼及其构筑的多孔材料奠定基础。

有机分子笼特有的结构和性质吸引着研究者，但是合成的困难使其种类和数量都比较少，也为其后续的研究造成了障碍。本项目探索两种路线合成酰腙类有机分子笼。一种是利用三聚氰氯为起始原料，分别与3-氨基-4-甲基苯甲酸甲酯和4-氨基苯甲酸甲酯反应合成了三脚架型羧酸酯；另一种是利用2,4,6-三（溴甲基）三甲基苯和3-羟基苯甲酸甲酯反应合成了三脚架型羧酸酯。然后三脚架型羧酸酯肼解合成了对应的三脚架型酰肼，最后和二醛进行醛肼缩合反应合成了有机分子笼。最后成功得到了7种酰腙类有机分子笼化合物，并通过核磁氢谱进行了表征，其中1种通过高分辨质谱确定了分子大小。由于酰肼前体和有机分子笼的的溶解性都很差，给后续的合成和表征工作都带来极大的困难，后续的研究工作都没有得到期望的结果。本项研究拓展了有机分子笼的种类，探索出了酰腙类有机分子笼的合成方法和合成条件，为后续此类有机分子笼的合成和性质研究提供了可能。