Controlling CO2‐Responsive Behaviors of Polymersomes Self‐Assembled by Coumarin‐Containing Star Polymer via Regulating Its Crosslinking Pattern

: An oligo(ethylene glycol)-based star polymer of N2 -(OEG-C)3 with fluorescent coumarin as hydrophobic end groups and dual tertiary amines as the star center is designed and synthesized. Owing to its amphiphilic nature of N2 -(OEG-C)3 , it will self-assemble into hollow vesicles with coumarin groups dispersed in the hydrophobic membrane and exhibits CO2 -responsive behavior due to the protonation of amine centers with CO2 . More importantly, coumarin moieties can either form non-crosslinking with γ-cyclodextrin via the 2/1 host-guest inclusion, or covalently photodimerized by 365 nm light, offering a tunable crosslinking pattern in the hydrophobic membrane and thus adjusting its CO2 -stimulated reorganization and disassembly behaviors of these vesicles in aqueous solution.