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

作者：Yuqi Cui, Jing‐Wang Cui, Jun‐Hao Zhou, Ke Zhao, Sihua Liu, Muhammad Asad Ziaee, Hao-Han Jiang, Jian Sun, Jian Sun, Yunhong Zhang, Jian‐Ke Sun, Jian‐Ke Sun · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c12545 · 被引用次数：16 · 研究领域：Ionic liquids properties and applications、Supramolecular Chemistry and Complexes、Organic and Molecular Conductors Research

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 markedl...