Regulation of Two-Dimensional Platelet Micelles by Dynamic Changing of Polymer Topological Architectures upon Light Irradiation

Abstract

Utilization of the crystallization-driven self-assembly (CDSA) approach has revolutionized the production of precisely controlled core–shell nanoparticles. However, the current scope of this robust method is limited to the linear chain architecture of crystallizable block copolymers (BCPs). This limitation raises intriguing questions about the impact of diverse topological chain architectures of crystallizable polymers on the CDSA behavior. Herein, we report that the topological chain architecture of styrylpyrene (SPy) moiety-modified BCPs bearing crystallizable poly(ε-caprolactone) (PCL) segments can be dynamically modulated via a [2 + 2] photocycloaddition reaction between SPy groups, yielding tadpole-shaped BCPs containing cyclic PCL segments. Due to the reversible photocycloaddition reaction upon light irradiation, the morphologies as well as fluorescence functionalities of two-dimensional (2D) platelets prepared by a seeded growth approach could be dynamically, reversibly, and precisely regulated by light irradiation. These findings provide valuable insights into the light-controlled manipulation of structurally and functionally diverse, topology-controlled multicomponent 2D assemblies, paving the way for potential applications in various scientific fields.