Peculiar Equilibrium Network Phases from Self-Assembly of Chiral Triblock Terpolymers

This work aims to systematically investigate the effect of chirality on the self-assembly of chiral triblock terpolymers. A series of triblock terpolymers, with chiral polylactide as the terminal block, were designed and synthesized to investigate their phase behavior. In addition to the compositional asymmetry that drives interface curvature, the chiral end block induces twisting at the microphase-separated interface. This twist not only expands the phase window for network formation but also enables homochiral evolution from molecule to phase, yielding network structures with controlled helicity. Furthermore, the introduction of conformational asymmetry can alleviate packing frustration, thereby stabilizing complex network phases. Consequently, with the enhancement of curvature and the alleviation of packing frustration, it is feasible to acquire the formation of complex stable network phases thermodynamically from the self-assembly of the chiral triblock terpolymers.