Conjugated Networked Poly(ionic liquid)-Accommodating Organic Cages: A Matter of Interhost Electron Communications

The construction of complex artificial hierarchical compartmentalized hosts that enable interhost electron communication to modulate─or even amplify─material properties remain a significant challenge. Herein, we report a supramolecular host-in-host assembly formed by electrostatic interactions between deprotonated hydroxyl-functionalized organic cages and bipyridinium bearing poly(ionic liquid)s (PILs). In this architecture, anionic cages are encapsulated within a polymeric network, creating a hierarchical structure that integrates discrete molecular hosts within an extended network. Benefiting from well-organized arrangement and cooperative functionality of dual-host components, UV light-triggered interhost electron transfer─from electron-rich O^- sites in the cages to electron-deficient pyridinium N⁺ centers in the PILs─is realized. This electronic interplay markedly enhances the material's physicochemical properties, yielding a ∼500-fold increase in conductivity and a high near-infrared (NIR) photothermal conversion (808 nm) efficiency of ∼82.2%. Incorporation of Pd clusters into the cage cavities further highlights the role of interhost electron communication in modulating the local catalytic environment─reshaping the electronic structure of Pd and the charge distribution around hydroxyl-lined cage windows to promote substrate orientation, adsorption and transport. Coupled with the nanofurnace effect of the nested architecture, these features collectively lead to markedly enhanced catalytic activity and selectivity in hydrogenation reactions.