Effect of Molecular Architecture and Symmetry on Self-Assembly: A Quantitative Revisit Using Discrete ABA Triblock Copolymers.

The inherent statistical heterogeneities associated with chain length, composition, and architecture of synthetic block copolymers compromise the quantitative interpretation of their self-assembly process. This study scrutinizes the contribution of molecular architecture on phase behaviors using discrete ABA triblock copolymers with precise chemical structure and uniform chain length. A group of discrete triblock copolymers with varying composition and symmetry were modularly synthesized through a combination of iterative growth methods and efficient coupling reactions. The symmetric ABA triblock copolymers self-assemble into long-range ordered structures with expanded domain spacings and enhanced phase stability, compared with the diblock counterparts snipped at the middle point. By tuning the relative chain length of two end blocks, the molecular asymmetry reduces the packing frustration, and thus increases the order-to-disorder transition temperature and enlarges the domain sizes. This study would serve as a quantitative model system to correlate the experimental observations with the theoretical assessments and to provide quantitative understandings for the relationship between molecular architecture and self-assembly.