Precisely Prepared Hierarchical Micelles of Polyfluorene‐<i>block</i>‐Polythiophene‐<i>block</i>‐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( 1 m ‐ b ‐ 2 n )) 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( 1 m ‐ b ‐ 2 n ) 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( 1 m ‐ b ‐ 2 n ) 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.