Binary Macromolecular Mesocrystals via Designed Block Copolymer Blends

The theoretical prediction that various binary macromolecular mesocrystals composed of A and C spheres could be formed by B1AB2CB3 pentablock terpolymers ( JACS 2014, 136, 2974–2977 ) offers a promising route to fabricate these intricately structured nanomaterials. However, experimental realization of this strategy has been impeded by the requirement of synthesizing precisely designed pentablock terpolymers. Here, we propose a conceptually new and technically simpler route to engineer binary macromolecular mesocrystals by using BA′/ABC/C′B ternary block copolymer blends that are designed to replicate the phase behavior of B1AB2CB3 pentablock terpolymers. Using self-consistent field theory, we show that the ternary blends exhibit similar self-assembly behaviors as the pentablock copolymers, forming various mesocrystals with controllable coordination numbers. This study offers a simpler alternative to fabricating novel macromolecular mesocrystals and introduces a general design principle for emulating multiblock copolymers by block copolymer blends.