Improving Stability, Crystallinity, and Photo‐Responsiveness of Supramolecular Frameworks by Surface Polymerization

Abstract

AbstractMetal–organic cage‐based photo‐responsive supramolecular frameworks (PSMFs) with permanent porosity have gained attention for their modular properties, controllable functionality, and light‐induced reversible responsiveness. However, their high porosity and photo‐responsive efficiency are often compromised due to poor structural stability upon solvent removal, limiting their potential applications. Here, a solution to overcome this challenge by employing a surface polymerization strategy using isophorone diisocyanate (IDI) to stabilize PSMF (PCC‐20t) is presented. This approach results in the composite of PCC‐20t@PolyIDI, which preserves crystallinity and permanent high‐porosity while avoiding structural collapse commonly observed in highly porous supramolecular frameworks. Moreover, compared to activated PCC‐20t, PCC‐20t@PolyIDI exhibits an 18.6‐fold increase in specific surface area. Remarkably, the structural variability of PCC‐20t@PolyIDI can be observed in the photo‐regulation behavior of CO2 capacity under the irradiation of vis‐ and UV‐light, showing a 27.9% change in adsorption amount for CO2 which is significantly higher than that of the activated PCC‐20t with 7.0% for CO2. Grand Canonical Monte Carlo simulations demonstrate the light‐regulated adsorption performance is attributed to the configuration transformation of azobenzene from trans‐ to buckling state. The findings may pave the way for stabilizing high‐porosity materials to simultaneously meet demands for high‐porosity and photo‐responsive efficiency.