Progressive Organization of Hydrogen‐Bonded Aramide Motifs via Foldamer–Macrocycle–Cage Architectures for Amplified Iodine Capture

ABSTRACT The rational design of high‐performance adsorbents is central to environmental remediation and separation. Yet whether assembling identical adsorption‐active motifs into higher‐order architectures can amplify the contribution of each motif beyond simple additivity remains unclear. Herein, the same hydrogen‐bonded aramide building block is progressively organized into acyclic foldamer, macrocycle, and cage architectures, establishing a motif‐conserved platform for isolating architectural effects on iodine capture. Across the designed architecture series, uptake capacity, kinetics, and retention improve stepwise from the acyclic structures to the macrocycle and further to the cage. Normalization to the number of aramide motifs reveals that the adsorption contribution of each motif also increases along this sequence, demonstrating non‐additive amplification rather than simple accumulation of binding sites. Notably, one cage captures up to 84 I 3 − per molecule in the presence of a 100‐fold excess of competing anions, representing the highest value reported for molecular adsorbents. Structural and computational analyses attribute this behavior primarily to strengthened motif‐level host–guest interactions generated by progressive architectural organization, while solid‐state packing modulates the distribution and accessibility of adsorption space. This work identifies progressive organization as a design paradigm for amplifying adsorption performance, offering insights into the development of advanced adsorbent materials.