多孔荧光配位聚合物的构筑及其对客体荧光传感研究

The recent intensive research of multifunctional metal?organic frameworks(MOFs) materials are concentrated in the fields of structural features,gas adsorption, photoluminscence,and magnetism, while the relevant research in photoluminent sensors is just launched, the compound based on the porous MOFs with fluorescent effect to guest molecules are rarely reported. It is planned to introduce photoluminent multidentate ligands including alkoxyl carboxylates, BODIPY-based pyridine and pyridiniumolates oxygen ion ligands into the MOFs framework by combination with metal ions or clusters,to explore the synthesis,topology structures and multifunctional properties of MOFs.The introduction of the luminescent organic linkers makes it possible for the materials to obtain luminescence and porosity simultaneously. This kind of MOFs-based material with an effect of fluorescence possess potentially significant application in the field of molecule sensor. We focus our study on the designing of ligands with specified geometry and the construction of fluorescent MOFs with interesting structures and multifunctional properties. The purpose of this study is to explore the structure-property relationship of the resulting MOFs. In order to reveal the preparation and relationship between structure and property, detect and establish the synthesis methods for molecular functional materials, and deep apprehension the physical principle of the structure-property relationship of the materials, more research on designing, synthesis and structure-property relationship are required,as well as the luminescent discoloration effect along with its underlying mechanism. This study would not only produce new MOFs with diverse structure, but also provide insight into the synthesis-structure-property relationship of such materials, which could be used for the rational design and synthesis of new type of MOFs materials with multifunctional properties.

目前对多功能配位聚合物的研究主要集中在气体吸附、荧光、磁性等领域,而在荧光传感方面的研究尚处于起步阶段，尤其是对客体有着荧光传感响应的鲜有报道。本项目拟选用能产生荧光的含烷氧基多齿羧酸、生色基BODIPY的吡啶、吡啶盐氧负离子配体，与金属离子配位构筑多孔荧光配位聚合物,将具有生色基团的有机配体引入骨架，使得构筑的化合物骨架同时有着多孔和荧光性质。由于多孔荧光配位聚合物对客体（分子或金属离子）具有良好的吸附功能，而且在吸附过程中往往会伴随着其物理、化学性质的变化，如骨架荧光波长、强度可能会发生变化，从而产生荧光传感响应，因此所构建的材料在传感领域有着重要的潜在应用价值，拓宽了其应用范围。本项目从功能需求出发，设计一定结构、功能的配体，探索如何通过调节配体来调节配位聚合物的结构与性能。总结出这类多功能材料的合成制备方法，揭示其结构与性能间的关系。为实现新型功能材料的定向设计和合成提供技术支撑。

微孔配位聚合物是一类重要的无机有机复合材料，其在气体吸附、催化、荧光传感等领域有着重要潜在应用。目前，如何定向设计合成这类材料仍是一项极具挑战性的工作。本课题基于能产生荧光的含烷氧基多齿羧酸、生色基BODIPY的吡啶、吡啶盐氧负离子配体，调控金属有机骨架结构，研究化合物对客体分子的荧光传感识别效应，从而拓宽金属有机骨架化合物的应用范围，探索和建立分子基功能材料的合成和制备方法，深入认识材料构效关系的物理本质。.在项目执行过程中，我们发现多例二维、三维多孔荧光金属有机骨架化合物，其中两例化合物对硝基苯类、三价铁离子具有双功能荧光传感效应。.到目前为止，在本项目支持下，已经在Inorganic Chemistry Communic 等期刊上共发表项目主持人为第一通讯人SCI论文4篇，中文核心1篇。培养研究生三名。