多孔有机笼的合成及衍生化

Synthesis and derivatization of porous organic cages

多孔有机笼(porous organic cages,POCs)作为一类具有永久空腔的三维有机分子,具有孔道结构有序、加工性良好、模块化等优点,已在气体吸附、分子分离、催化等领域展现了巨大应用潜力,成为多孔材料科学的前沿研究方向之一.近年来,利用动态共价化学,许多拓扑结构新颖和功能丰富的POCs被成功合成报道.然而,与多孔框架材料不同,全封闭结构的POCs需要构建块间有更精确的匹配性,导致了POCs自下而上设计合成相对困难,难以系统地进行功能化.为解决上述瓶颈问题,近年来领域的研究者们发展了一系列合成后修饰策略来扩展POCs的结构与功能.此外,POCs结构中丰富的有机官能团赋予了材料被进一步拓展为高级结构的可能性,如将POCs转化为多孔框架材料如金属有机框架、共价有机框架、氢键有机框架等,这些研究将有利于整合多种材料的优势并推动多孔材料领域的发展.基于此,本文从POCs的合成、合成后修饰以及结构转化等方面对多孔有机笼的合成及衍生化进行综述.

Porous organic cages(POCs),as a class of three-dimensional organic molecules with permanent cavities,have advantages such as ordered pore structure,good processability,and modularity.They have shown great potential in gas adsorption,molecular separation,catalysis,and other fields,becoming one of the cutting-edge research directions in porous material science.In recent years,a large number of POCs with novel topological structures and rich functions have been successfully synthesized using dynamic covalent chemistry.However,unlike porous framework materials,fully enclosed POCs require more precise matching of building blocks,which makes it relatively difficult to design and synthesize,systematically functionalize POCs via bottom-up approach.In order to address the aforementioned bottleneck issues,researchers in the field have developed a series of post-synthetic modification strategies to expand the structure and function of POCs in recent years.In addition,the rich organic functional groups of POCs endow materials with the possibility of further expanding into advanced structures,for example,converting POCs into porous framework materials such as metal organic frameworks,covalent organic frameworks,hydrogen-bonded organic frameworks,etc.These studies will be beneficial for integrating the advantages of multiple materials and promoting the development of the field of porous materials.Based on above,this article will summarize the synthesis,post-synthetic modification and structural transformation of POCs.