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Abstract Porous organic cages (POCs) represent a new class of microporous materials with an impressive breadth of potential applications. One of their many advantages is the degree of tunability of cage properties, similar to that seen in more established microporous materials like metal‐organic frameworks. In this work, a prototypical POC, CC3, is used to explore the potential to tune cage properties via post‐synthetic dynamic covalent chemistry. Ethylenediamine, the linker used in another POC, CC1, was partially substituted into the CC3 cage structure to varying degrees based on the starting relative molar ratios. The resulting products were investigated for the relative distribution of the two linkers, crystallinity, and surface area. It was found that even when small amounts of other compatible diamine linkers are introduced, they substitute into the existing cages, although some structural products are apparently favored over others within the reactant ratios investigated.more » « less
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