Dynamic Covalent Radical Recombination for the Assembly of Tuneable Responsive Porous Organic Cages

, as confirmed by gas sorption experiments, arising from narrow pore apertures and strong host-guest interactions. Both cages display reversible mechano- and thermochromic behaviour. Moreover, the combination of a highly dynamic bond formation process with three-dimensional preorganisation of the cage enables efficient self-healing, which is markedly accelerated upon exposure to THF vapour. Collectively, these results establish radical recombination as an unexplored dynamic covalent motif for the synthesis of responsive organic cage architectures, enabling substituent-dependent fine-tuning of topology, stability, and material function through simple substituent modification.