A thiol-terminated diblock copolymer with a crystallizable core-forming metalloblock: Synthesis by sequential anionic polymerization and solution self-assembly

A new class of diblock copolymers, PFDMS-b-PPS (PFDMS = polyferrocenyldimethylsilane, PPS = polypropylene sulfide), with a crystallizable PFDMS block and a thiol-terminated reactive-oxygen-species responsive PPS block were synthesized via carbanion-pump-mediated sequential anionic polymerization. Well-defined rod-like micelles were prepared from the self-assembly of the block copolymers in dimethylformamide, a selective solvent for the PPS block. Seeded growth of the rod-like micelles led to the formation of longer micelles or block co-micelles. In this way, triblock co-micelles were prepared with a PFDMS₃₅-b-PPS₁₀₀₀ center block and PFDMS₂₂-b-P2VP₁₅₄ end blocks. We demonstrated the functionalization of PFDMS-b-PPS micelles with CdSe quantum dots and spatially selective functionalization of the PFDMS-b-P2VP end blocks of the triblock co-micelles with Fe₃O₄ or gold nanoparticles.