Manipulating the ABCs of self-assembly via low-{chi} block polymer design [Chemistry]

Block polymer self-assembly typically translates molecular chain connectivity into mesoscale structure by exploiting incompatible blocks with large interaction parameters (χ_ij). In this article, we demonstrate that the converse approach, encoding low-χ interactions in ABC bottlebrush triblock terpolymers (χ_AC ≲≲ 0), promotes organization into a unique mixed-domain lamellar morphology, which we designate LAM_P. Transmission electron microscopy indicates that LAM_P exhibits ACBC domain connectivity, in contrast to conventional three-domain lamellae (LAM₃) with ABCB periods. Complementary small-angle X-ray scattering experiments reveal a strongly decreasing domain spacing with increasing total molar mass. Self-consistent field theory reinforces these observations and predicts that LAM_P is thermodynamically stable below a critical χ_AC, above which LAM₃ emerges. Both experiments and theory expose close analogies to ABA′ triblock copolymer phase behavior, collectively suggesting that low-χ interactions between chemically similar or distinct blocks intimately influence self-assembly. These conclusions provide fresh opportunities for block polymer design with potential consequences spanning all self-assembling soft materials.