Post-synthetic modification of porous organic cages

Porous organic cages (POCs) represent an emerging class of organic materials with intrinsic porosity. They have found various applications in supramolecular chemistry, materials science, and many other related disciplines, which stem from their molecular host-guest interactions, intrinsic and inter-cage porosity in solid state as well as the diversity of functionalities. Post-synthetic modification (PSM) has emerged as a highly viable strategy for broadening the functions and applications of POCs. Intricate structures, enhanced stability, tunable porosity and guest binding selectivity and sensitivity have been realized through PSM of POCs, which cannot be directly achieved via the predesign and bottom-up assembly from small molecule building blocks. For example, an unstable imine-linked POC can be transformed into a more stable amine-linked cage, whose cavity size can be further tuned by selective binding of some amine groups, offering unusual gas adsorption selectivity for noble gases (e.g., preferred uptake of Xe over Kr). Such improvement of the chemical stability and gas separation properties through the consolidation of linkage and adjustment of porosity is challenging to achieve otherwise. In this tutorial review, we highlight the importance and impact of PSM in engineering the properties of POC molecules, their frameworks, and composites going beyond the direct predesign synthetic strategy. The primary PSM strategies for exploring new compositions, functions and applications as well as their structure-property relationship have been summarized, including cage-to-cage transformation at the molecular level, covalent or noncovalent assembly of POCs into frameworks, and formation of composites with guest species or other additives encapsulated.