Polyferrocene‐Based Cubosomes: Conversion to Magnetic Mesoporous Microparticles, Supramolecular Modification, and Oxidation Response

Abstract Polymer cubosomes (PCs) are an emerging class of mesoporous microparticles that are produced through solution self‐assembly of highly asymmetric block copolymers (BCPs). They proved useful for encapsulation or templating replicas for catalysis and energy storage. Although PCs made from BCPs with intrinsic functions such as response to stimuli, degradation, or coordination canopen their use for more diverse applications, reports on PCs with innate functions are still rare. Herein, PCs based on organometallic BCPs bearing pendant ferrocene moieties is reported. The poly(ethylene oxide)‐ block ‐poly(2‐(methacryoyloxy)ethyl ferrocene carboxylate) BCPs (PEO ₄₄ ‐ b ‐PFcEMA _x ) with highly asymmetric weight fraction is synthesized in favor of the hydrophobic block ( x = 76–245). Of these, PEO ₄₄ ‐ b ‐PFcEMA ₉₆ assembled into PCs with an average particle diameter of 1.82 ± 0.48 µm, a double diamond lattice, and a pore diameter of ≈30–40 nm. The functionality of these PCs are showcased by i) templating metal oxide replica with concurrent decoration of magnetic iron oxide upon calcination, ii) supramolecular modification of the PC wall via host‐guest chemistry, and iii) degradation of the PC structure on demand through oxidation. Exploring these and other block chemistries enriches thetoolbox for PC applications and fosters theunderstanding about PCs by identifying differences or communalities in formation mechanisms and particle structure.