Host‐in‐Host Complexation: Activating Classical Hosts through Complete Encapsulation within an M₉L₆ Coordination Cage

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This study reports a method for enhancing the functions and properties of traditional organic macrocyclic hosts by fully encapsulating them within a large M 9 L 6 cage to form host‐in‐host complexes. Within the cage host, the macrocyclic organic hosts with electron‐rich aromatic rings, such as cyclotriveratrylene and calix[8]arene, adopt specific orientations enhancing their inherent molecular recognition abilities. Due to the high crystallinity of the M 9 L 6 cage, the guest encapsulation behavior of the host‐in‐host complexes can be observed by X‐ray structural analysis.