In-situ isomerization and reversible self-assembly of photoresponsive polymeric colloidal molecules enabled by ON and OFF light control

Photocatalytic colloids enable light-triggered nonequilibrium interactions and are emerging as key components for the self-assembly of colloidal molecules (CMs) out of equilibrium. However, the material choices have largely been limited to inorganic substances and the potential for reconfiguring structures through dynamic light control remains underexplored, despite light being a convenient handle for tuning nonequilibrium interactions. Here, we introduce photoresponsive N,O-containing covalent organic polymer (NOCOP) colloids, which display multi-wavelength triggered fluorescence and switchable diffusiophoretic interactions with the addition of triethanolamine. Our system can form various flexible structures, including AB_n-type molecules and linear chains. By varying the relative sizes of active to passive colloids, we significantly increase the structural diversity of A₂B₂-type molecules. Most importantly, we demonstrate in-situ transitions between different isomeric configurations and the reversible assembly of various structures, enabled by on-demand light ON and OFF control of diffusiophoretic interactions. Our work introduces a new photoresponsive colloidal system and a novel strategy for constructing and reconfiguring colloidal assemblies, with promising applications in microrobotics, optical devices, and smart materials.