Multi-Armed Micelles and Block Co-micelles via Crystallization-Driven Self-Assembly with Homopolymer Nanocrystals as Initiators

We report the preparation of multi-armed micelles and block co-micelles using the crystallization-driven self-assembly of crystalline-coil polyferrocenylsilane block copolymers from nanocrystals of the homopolymer. The resulting multi-armed micelles possessed hierarchical multipod structures with monodisperse and tunable arm lengths. The termini of the arms remained active to the addition of further block copolymer unimers, and multi-armed block co-micelles with segmented arm chemistries and variable segment sequences were prepared. Coronal cross-linking followed by nanocrystal dissolution led to the release of non-centrosymmetric AB cylindrical diblock co-micelles.