Synergistic Effect of Stretched Bridging Block and Released Packing Frustration Leads to Exotic Nanostructures

The self-assembly of amphiphilic macromolecules into various mesocrystals has attracted abiding interest. Although many interesting mesocrystals have been achieved, mesocrystals of a low coordination number (CN) such as simple cubic are rarely reported. Here we purposely design an AB-type multiblock copolymer to target exotic spherical phases of low CNs. Self-consistent field theory reveals that two sophisticated mechanisms are realized in the copolymer, that is, stretched bridging block and released packing frustration, synergistically leading to the formation of three spherical phases with extremely low CNs, including the simple cubic spheres (CN = 6), the cubic diamond spheres (CN = 4), and normally aligned hexagonal-packing spheres (6 < CN < 8) in a considerable parameter region. Moreover, we demonstrate that these exotic phases are hard to be stabilized by either of the two mechanisms individually.