Molecular Recognition Directs Charge‐Transfer Evolution in an Adaptive Macrocyclic Host–Guest Solid

ABSTRACT Adaptive supramolecular solids capable of dynamically regulating their structures and functions in response to molecular stimuli are important for responsive materials, yet controllable guest release and regeneration through structural evolution remain challenging. Herein, we report a dynamic macrocyclic charge‐transfer (CT) system constructed from electron‐rich perethylated pillar[5]arene ( EtP5 ) and electron‐deficient F4TCNQ , in which guest molecules direct donor–acceptor evolution. The structurally disordered EtP5–F4TCNQ CT‐active solid undergoes multiple guest‐dependent transformations, including framework ordering, competitive disruption, and cooperative reconstruction, giving rise to distinct structural and electronic states with tunable CT interactions. Single‐crystal analysis reveals the structural origins of these divergent pathways, while mixed‐guest studies demonstrate that molecular competition and cooperation reshape the CT evolution landscape. Notably, guest‐dependent CT states regulate near‐infrared absorption and photothermal conversion, thereby governing subsequent guest‐release pathways. A strongly coupled CT state generated by toluene‐directed reconstruction enables rapid light‐driven guest release through a self‐enhancing interplay between structural evolution and photothermal conversion, whereas the CT‐deficient state regenerates through spontaneous dissociation or guest‐induced framework reconstruction. This work establishes a CT‐state‐governed adaptive solid that couples molecular recognition, structural evolution, and energy conversion, providing a platform for selective molecular capture, vapochromic sensing, and controllable guest release and regeneration.