Thermally Switchable Photoactivity in Azobenzene‐Functionalized DNA Condensates

Soft materials capable of responding to diverse environmental stimuli are fundamental to advancing soft robotics and intelligent biomedical devices, enabling adaptive, life‐like functions. Here, multimodal photothermal adaptability is reported in azobenzene‐conjugated DNA condensates assembled via liquid‐liquid phase separation (LLPS). These coacervates exhibit a striking temperature‐dependent inversion of their photo‐response: at elevated temperatures, the liquid‐like droplets deform under visible light and dissolve under ultraviolet (UV) light, whereas at lower temperatures, the gel‐like condensates are reshaped by UV light while remaining inert to visible light. This unique bidirectional control is attributed to the synergy of confined azobenzene photochemistry within DNA duplexes and a pronounced isomer‐dependent shift in the system's glass transition and melting temperatures. This platform of multi‐responsive photofluids opens new avenues for applications demanding exquisite spatiotemporal control.