Discrete Miktoarm Star Block Copolymers with Tailored Molecular Architecture

Molecular architecture is a critical factor in regulating phase behaviors of the block copolymer and prompting the formation of unconventional nanostructures. This work meticulously designed a library of isomeric miktoarm star polymers with an architectural evolution from the linear-branched block copolymer to the miktoarm star block copolymer and to the star-like block copolymer (i.e., 3AB → 3(AB₁)B₂ → 3(AB)). All of the polymers have precise chemical composition and uniform chain length, eliminating inherent molecular uncertainties such as chain length distribution or architectural defects. The self-assembly behaviors were systematically studied and compared. Gradually increasing the relative length of the branched B₁ block regulates the ratio between the bridge and loop configuration and effectively releases packing frustration in the formation of the spherical or cylindrical structures, leading to a substantial deflection of phase boundaries. Complex structures, such as Frank–Kasper phases, were captured at a surprisingly higher volume fraction. Rationally regulating the molecular architecture offers rich possibilities to tune the packing symmetry of block copolymers.