有机分子笼成晶机制：从分子到固体的原位固体核磁共振研究

Porous materials play an important role in adsorption, catalysis, separation, storage and other fields. Organic molecular cages (POCs) are a new kind of porous organic materials, not only featuring molecular porosities, but also retaining the solubility of molecules. With the advantages of "porous solid" and "porous liquid", it has important potential applications in the field of gas adsorption and separation, molecular recognition, molecular reactor etc. However, there is a great lack of information on the crystallization mechanism and structure-activity relationship of the POCs materials at present.. The change of molecular motion is the core reason for dynamic behaviors and phase change. While solid-state nuclear magnetic resonance (SSNMR) is especially good at structural and dynamic analysis of crystalline materials. In this project, the in-situ dynamic SSNMR will be utilized to investigate the crystallization process, skeleton kinetics and solvent-host interactions of a series of selective spin-labeled POCs. The pore structure and host-guest relationship, both in solid and liquid phases, will be further explored through the SSNMR technology with adsorption of probe molecules, such as 129Xe, SF6, etc. Our investigations will provide theoretical basis and guidancea for understanding and rational designing of intelligent porous organic materials.

多孔材料在吸附、催化、分离、存储等领域中扮演着重要角色。有机分子笼（POCs）作为一类新兴的有机多孔材料，具有分子自身多孔性的同时也保留了分子的可溶性。兼具“多孔固体”和“多孔液体”的优势，在气体吸附和分离、分子识别、分子反应器等领域具有重要的应用潜力。然而，该类新型材料的成晶机理与构效关系信息有待进一步探索。. 分子运动性变化是材料动态变化和物相改变的核心原因，而固体核磁共振尤其擅长于晶型材料的结构和动力学分析。本项目拟通过原位固体核磁考察选择性自旋标记的系列POCs的成晶过程、骨架动力学及其与溶剂的作用机制，并进一步通过核磁探针分子（129Xe, SF6）技术探究材料中的孔道结构和主客体构效关系。本项目的开展将为理解和设计智能有机多孔材料提供理论基础和指导。

有机分子笼（POCs）作为一类新兴的有机多孔材料，具有分子自身多孔性的同时也保留了分子的可溶性。本项目首先合成并表征了四种晶型有机分子笼材料，接着采用固体核磁碳谱（13C CP/MAS NMR）和变温氘谱技术（VT 2H NMR）研究了晶型有机孔材料的分子结构与骨架动力学行为，同时利用固体核磁氙谱（129Xe NMR）考察了晶型孔道的腔体均一性，之后还进一步展开了有机孔材料的孔道腔体限域与负载团簇功能化研究，并取得良好的催化效果。项目研究了晶型有机孔材料的晶化构筑、分子结构、骨架动力学、孔道限域特性以及催化功能化应用，为理解、设计和应用有机多孔材料提供了实验基础。