Precisely Prepared Hierarchical Micelles of Polyfluorene‐block‐Polythiophene‐block‐Poly(phenyl isocyanide) via Crystallization‐Driven Self‐Assembly

Abstract

The precise preparation of hierarchical micelles is a fundamental challenge in modern materials science and chemistry. Herein, poly(di‐n‐hexylfluorene)‐block‐poly(3‐tetraethylene glycol thiophene) (poly(1m‐b‐2n)) diblock copolymers and polyfluorene‐block‐polythiophene‐block‐poly(phenyl isocyanide) triblock copolymers were synthesized using a one‐pot process via the sequential addition of corresponding monomers using a Ni(II) complex as a single catalyst for living/controlled polymerization. The crystallization‐driven self‐assembly of amphiphilic conjugated poly(1m‐b‐2n) led to the formation of nanofibers with controlled lengths and narrow dispersity. The block copolymers exhibited white, yellow, and red emissions in different self‐assembly states. By using uniform poly(1m‐b‐2n) nanofibers as seeds, introducing the polyfluorene‐block‐polythiophene‐block‐poly(phenyl isocyanide) triblock polymer as a unimer in the seed growth process, and adjusting the structure of the poly(phenyl isocyanide) block and the polarity of self‐assembly solvent, A‐B‐A triblock micelles, multiarm branched micelles, and raft micelles were prepared.