Diblock copolymer micelles with patches in polyhedral configurations mimicking atomic valence structures†

Colloidal particles can act as artificial atoms in the synthesis of colloidal molecules that resemble molecular structures, provided they mimic valence behavior and atomic bonding. Chemically or structurally distinct patches on their surfaces can offer valence-like behavior, enabling inter-patch bonding. In this study, we demonstrate that patchy micelles of diblock copolymers can mimic atomic valence configurations and bond formation. We first synthesized a series of diblock copolymers to form spherical micelles with varying corona-to-core ratios. Then, we induced patches in linear, triangular, tetrahedral, trigonal bipyramidal, and octahedral configurations, mimicking atomic valence shapes, by crosslinking the core and modifying the solvent. Additionally, we confirmed that the size of patchy micelles, particularly those with a tetrahedral configuration, could be controlled by adjusting the total molecular weight of copolymers while preserving the corona-to-core ratio. Furthermore, by utilizing bond formation through the merging of patches, we successfully constructed colloidal molecules using multi-patch and single-patch micelles.