Multi-Chamber Dynamic Molecular Crystal Microcapsules for Payload Encapsulation and Controlled Release

Abstract Crystalline self-assembly offers a powerful route to ordered organic materials with well-defined structures and morphologies. Despite substantial advances in controlling crystal habit, organic single crystals with precisely engineered architectures, particularly those with fully enclosed internal cavities, remain exceptionally rare and challenging to fabricate. Here, we report a one-pot strategy that uses an optimized aqueous multisurfactant crystal growth approach to produce microcapsules with programmable numbers and sizes of sealed internal compartments. A simple model captures the qualitative aspects of this phenomenon by positing diffusion-limited growth coupled with asymmetric surfactant inhibition. The microcapsule voids are contained within a single crystal domain, enabling encapsulation and long-term storage of diverse components, including water-soluble dyes, hydrogen peroxide, and nanoparticles, within separate chambers of a multichambered crystalline microcapsule. The encapsulated species remain fully isolated and leak-tight for over 200 days. Visible-light irradiation (400–580 nm) causes photoactive molecules within the crystal matrix to undergo [2 + 2] photocycloaddition, inducing photomechanical disintegration at specific locations. This capability enables on-demand release of stored contents ranging from inorganic nanoparticles to small molecules. For example, the triggered release of H2O2 or Fe3+ gives rise to chemiluminescent reactions in localized regions near the ruptured crystals. This work establishes a new design paradigm for dynamic photoresponsive molecular crystals with programmable internal architectures and emergent functionalities.