靶向识别贵金属离子的金属有机骨架材料的设计与合成

Detection and retrieval of noble metal ions has a significant impact on the development of biomedicine, environmental protection and electronics manufacturing. In this proposal, we will take a crosscutting approach that integrates the knowledge of organic synthesis, crystal engineering, solution sensing technology and solid-state chemistry. Our strategy here is to develop a class of robust and versatile metal-organic frameworks for the noble metal targeted applications， based on the predesigned multifunctional organic ligands. The key idea is to install two distinct sets of organic functions on molecular building blocks, one is chemically hard carboxyl group and the other is chemically soft alkene (or alkyne) thioether group. According to hard and soft approach, chemically hard metal ions will selectively bind to carboxyl groups to form a robust metal-organic framework, while the soft alkene (or alkyne) thioether groups remain free standing functionalizing the pores. Further investigation of the cross covalent coupling of the alkyne-functionalized metal-organic frameworks, aims for high stability, highly efficient detection and retrieval of noble metal ions. Moreover, we will look into the influence of the pore size, internal environment and photoluminescence on its sensing efficiency. We will then explore the targeted application for noble metal ions with the separated solids. To conclude, we will summarize the correlationship between the well-defined structures and their properties, in order to provide guidance for the design of new functional materials.

贵金属离子的检测和回收对于生物制药、环境保护和电子制造等行业都具极其重要的意义。本研究将综合利用有机合成化学、晶体工程、溶液传感技术和固态材料化学等多个学科的研究方法，通过有机功能配体的设计合成，实现对特定贵金属离子具有靶向识别功能的金属有机骨架材料的定向组装。本项目拟利用烯（炔）基硫醚芳香羧酸作为功能性配体，根据软硬酸碱理论，硬酸金属离子会选择跟羧基形成三维开放式金属有机骨架，而烯（炔）基硫醚游离在孔道中并用于功能化修饰。开展炔基功能化金属有机骨架化合物的共价偶联研究，以期提高目标化合物的稳定性及对贵金属离子传感功能的灵敏性和选择性。重点考察目标骨架材料不同孔径尺寸、孔道内部环境及光致发光性能对特定贵金属离子传感功能的影响，探索结构的变化对其靶向识别性能的影响，构建结构与性能间构效关系，为开发新型识别材料提供更多的科学依据。

贵金属离子的检测和回收对于生物制药、环境保护和电子制造等行业都具极其重要的意义。本项目综合利用有机合成化学、晶体工程、溶液传感技术和固态材料化学等多个学科的研究方法，通过有机功能配体的设计合成，实现硫醚功能化金属有机骨架材料的定向组装。本项目合成了系列含烯基硫醚芳香羧酸作为功能性配体，根据软硬酸碱理论，硬酸金属离子会选择跟羧基形成三维开放式金属有机骨架，而烯基硫醚游离在孔道中并用于功能化修饰。开展了目标功能配位聚合物的荧光性能、对小分子的靶向识别性能外，还大量开展了目标功能配位聚合物的导电性能、催化性能等相关研究。同时，还发展了硫醚-芳香羧酸功能配体的现代合成方法，攻克了硫醇-金属配位网络难结晶的问题，开发了几个有潜在应用前景的有机小分子荧光探针，探索了基于硫醇-共价有机框架的定向合成。此外，还基于前期工作继续探索了联吡唑配位聚合物的构筑及其导电性能研究。迄今为止，已发表高水平论文十七篇，申请专利十余项，初步构建了结构与性能间构效关系，为开发新型识别材料提供更多的科学依据。