Thermodynamically stable plumber’s nightmare structures in block copolymers

Block copolymer self-assembly affords diverse nanostructures, spanning from spheres and cylinders to networks, offering meticulous control over properties and functionalities at the nanoscale. However, creating thermodynamically stable network structures with high packing frustration remains a challenge. In this study, we report a methodology to access diverse network structures such as gyroid, diamond, and primitive phases from diblock copolymers using end group and linker chemistry. The stability of the medial packing of polymer chain ends (plumber's nightmare structure) over skeletal aggregation (gyroid) is attributed to the interplay between the strength of the end-end interactions and the initial shape of the curvature. Our study establishes an approach to develop tailored network structures from block copolymers, providing an important platform for using block copolymers in nanotechnology applications.