基于UPy/NAPy相互作用的超分子胶囊的构筑与性质研究(一)

The current proposal aimed at construction of homo and hetero supramolecular capsules by using excellent hydrogen bonding building blocks----UPy/NAPy combination as driving force and calix[4]resorcinarene-based cavitand and calix[4]pyrrole as skeletons. Through the study of encapsulation capability of guest molecules especially fullerenes by these capsules, we hope to induce the mechanism of the self-assembly process and guests in-out of the capsules. The structure-encapsulation property relationship between capsules and fullerenes is an important goal of this project. Based on the encapsulation study, an efficient and quick method for separating fullerene mixtures is expected. Furthermore, construction of a capsule with expanded cavity for encapsulation of a C120 molecule and two C60 molecules simultaneously is another goal. We plan to study particular chemical-physical phenomena in confined space and aim to use this kind of supramolecular capsules as chambers for chemical reactions with high selectivity. The last task is the construction of capsule-based supramolecular polymer for linear arrangement of fullerenes to study their chemical-physical properties. This will provide new ideas and platforms for the construction of new materials.

本申请课题选用优秀的氢键键合单元UPy/NAPy相互作用为基本作用力，以构象固定的雷琐酚杯芳烃和杯吡咯为骨架，构筑多重氢键锁住的同体/异体超分子胶囊；研究这些胶囊对客体特别是富勒烯分子的包结性能，揭示自组装过程以及客体进出胶囊的机理，总结出胶囊结构对包结富勒烯分子能力差异的规律性认识，并以此为基础发展高效快捷分离富勒烯混合物的方法；构筑空腔可拓展的胶囊，研究其对体积较大的富勒烯分子C120以及两个C60的包结行为，研究受限空间内独特的物理化学现象，并探索这类胶囊作为选择性化学反应容器的应用；构筑基于胶囊的超分子聚合物，定向排列富勒烯分子，研究其独特的物理化学性质，为新材料的研制提供新的思路和平台。

本课题发展了四种类型的多氢键键合的超分子胶囊体系和一类新型的基于配体-金属配位作用的超分子胶囊体系。（1）基于四脲基嘧啶酮雷琐酚杯芳烃的同体超分子胶囊。该胶囊对C60分子具有强的键合能力；以此为基础，我们开发了分离纯化富勒烯的方法。（2）除了自身形成同体胶囊以外，四脲基嘧啶酮雷琐酚杯芳烃还能与四二酰胺萘啶雷琐酚杯芳烃形成异体胶囊。（3）采用杯吡咯为骨架，在胶囊空腔内部引入了极性NH位点，为客体精确定位提供基础。（4）以Hamilton受体-三聚氰酸客体作用为键合作用力，我们还发展了一种新型的异体超分子胶囊。两个半球未混合前均不存在聚集，这使得研究大大简化。此外我们还发展了（5）基于三联吡啶-锌离子配位作用的超分子胶囊。对这些胶囊性质的深入探索，可能导致在分离、催化、分子反应容器、药物缓释等方面的实际应用。