基于动态共价亚胺键的大环和分子笼的构筑与性质

This project is based upon the combination of latest developments on Schiff-base macrocyclic chemistry and organic molecular cages, and directed by the nature of Dynamic Imine Covalent Bonds. We are planning to design and synthesize a series of flexible extended dialdehydes with different functional pendant arms as well as rigid aromatic multi-aldehydes and use them as precursors to react with a family of chiral/achiral aromatic/alkyl diamines/multi-amines in the presence or absence of certain metal template ions so as to produce pendant-armed Schiff-base macrocyclic complexes and organic cage compounds with different molecular length, symmetry and flexibility. Post-modification (such as supramolecular assembly, introduction of second cation or bridging units, and reduction of Schiff-base C=N to C-N by NaBH4) would be used to some specific macrocyclic metal complexes and cage compounds to further change their structures. We will pay special attention to the possible properties for these target compounds such as guest molecular and ionic recognition, selective gas adsorption and separation, sensitizers of rare earth ion emission and, antimicrobial activities and fluorescence sensors. For example, we have constructed a Na(I) network of cages from discrete molecular cages exhibiting good hydrolytic stability and enhanced co2 adsorption capacity (Angew. Chem., Int. Ed., 2017, 56, 7787, Hot Paper).

结合席夫碱大环化学和有机分子笼的最新研究热点，利用亚胺键的动态共价键特性，针对金属离子模板法制备席夫碱大环配合物和非模板法制备席夫碱多孔有机笼化合物，分别设计合成具有不同功能臂的柔性扩展二醛和刚性扩展芳香多醛前驱体，与二胺/多胺作用构筑具有不同数目亚胺键，不同尺寸、核数、对称性和空间构型的席夫碱金属大环配合物和有机分子笼化合物，还可以通过后修饰手段（如大环配合物和有机笼的超分子组装、引入第二阳离子或桥联阴离子以及亚胺键键还原等）进一步改变大环结构，对其离子/分子识别与超分子组装、气体选择性吸附与分离、敏化稀土离子发光、抗菌活性与荧光传感等相关性质进行详细的探究，希望在气体吸附材料和光电功能材料方面取得重点突破。例如我们从零维席夫碱有机笼构筑了弱配位Na(I)连接的多级孔道的三维框架，展现出良好的水解稳定性和CO2吸附能力（2017年Angew. Chem., Int. Ed.热点文章）。

结合席夫碱大环化学和有机分子笼的最新研究热点，利用亚胺键的动态共价键特性，针对金属离子模板法制备席夫碱大环配合物和非模板法制备席夫碱多孔有机笼化合物，分别设计合成了系列具有不同功能臂的柔性扩展二醛和刚性扩展芳香多醛前驱体，与二胺/多胺作用构筑具有不同数目亚胺键，不同尺寸、核数、对称性和空间构型的席夫碱金属大环配合物和有机分子笼化合物。此外，通过后修饰手段（如大环配合物和有机笼的超分子组装、引入第二阳离子或桥联阴离子以及亚胺键键还原、转金属和去金属等）进一步改变大环结构，对其离子/分子识别与超分子组装、气体选择性吸附与分离、敏化稀土离子发光、抗菌活性与荧光传感等相关性质进行了详细的探究，在该项目资助下申请人以责任作者身份共发表SCI科研论文31篇。包括Green Chem. 1篇；Chem. Commun. 2篇；Inorg. Chem. 3篇；Dyes Pigm. 13篇；Dalton Trans. 邀请综述1篇；J. Phys. Chem. C 3篇等。