A Supramolecular‐Nanocage‐Based Framework Stabilized by π‐π Stacking Interactions with Enhanced Photocatalysis

Abstract π frameworks, defined as a type of porous supramolecular materials weaved from conjugated molecular units by π‐π stacking interactions, provide a new direction in photocatalysis. However, such examples are rarely reported. Herein, we report a supramolecular‐nanocage‐based π framework constructed from a photoactive Cu(I) complex unit. Structurally, 24 Cu(I) complex units stack together through π‐π stacking interactions, forming a truncated octahedral nanocage with sodalite topology. The inner diameter of the nanocage is 2.8 nm. By sharing four open faces, each nanocage connects with four equivalent ones, forming a 3D porous π framework ( π‐2 ). π‐2 shows good thermal and chemical stability, which can adsorb CO 2 , iodine, and methyl orange molecules. More importantly, π‐2 can serve as a photocatalyst for hydrogen evolution reaction. With ultrafine Pt subnanometer particles (0.9±0.1 nm) incorporated into the nanocages as a co‐catalyst, the hydrogen evolution rate reaches a record‐high value of 524012 μmol/g Pt /h in the absence of any additional photosensitizers. The high photocatalytic activity can be ascribed to the ultrafine size of the Pt particles, as well as the fast electron transfer from π‐2 to the highly active Pt upon illumination. π‐2 represents the unique stable supramolecular‐cage‐based π framework with excellent photocatalytic activity.