Fluorous Cylindrical Micelles of Controlled Length by Crystallization-Driven Self-Assembly of Block Copolymers in Fluorinated Media

Fluorous solvents have recently found broad applications in medical treatments as well as catalytic transformations, yet the controlled self-assembly of nanomaterials in fluorinated media has remained a challenge. Herein, we report the synthesis of block copolymers containing a crystalline polyferrocenylsilane metalloblock and a highly fluorinated coil block and their controlled self-assembly in fluorinated media. Using the crystallization-driven self-assembly approach, cylindrical micelles have been prepared with controlled lengths and narrow length polydispersities by self-seeding. Finally, by partial functionalization of these block copolymers with fluorescent dye molecules, we show that well-defined, functional nanomaterials can be obtained in the fluorous phase.