Water-Soluble Micelles with a Polyferrocenylsilane Core for Reductive Synthesis of Nanomaterials

Living crystallization-driven self-assembly (CDSA) has developed as a versatile and programmable strategy for constructing multidimensional micellar nanostructures. While corona modification facilitates the tailored fabrication of diverse functional materials, the crystalline core is substantially underexplored for postassembly functionalization. Herein, we find that water-soluble polyferrocenylsilane-b-poly(2-vinylpyridine) micelles featuring a quaternized corona allow full compatibility and permeation of hydrophilic oxidants, thereby enabling in situ redox reactions with the reductive polyferrocenylsilane core. This permits the direct preparation of a series of metallic nanomaterials, such as MnO₂, Fe(OH)₃, Pt, Pd, and Ru, under ambient conditions with the addition of anionic oxidants including MnO₄^-, FeO₄^2-, PtCl₄^2-, PdCl₄^2-, and RuCl₅^2-. On the contrary, when cationic oxidants (e.g., Ag⁺, Au³⁺, and Rh³⁺) are added, the redox reaction is impeded by the electrostatic repulsion with the positively charged corona. Interestingly, the addition of electrolyte (e.g., KNO₃) would remarkably relieve the kinetic barrier of ion diffusion and hence facilitate the formation of metal nanorods or nanoparticle chains. Moreover, in situ redox reactions on micellar brushes fabricated through surface-initiated living CDSA further enable the formation of vertical MnO₂ nanoarray and Ag nanochain networks, showing appealing potential applications in aqueous zinc ion batteries and flexible electronic devices.