Self-assembly of three-component bolaform giant surfactants with branched architectures

Abstract

Branched architecture profoundly influences the physical properties of polymers, making it an important topic in the field of polymer science. Herein, we report a facile synthetic strategy to introduce one site-specific side chain at the junction point to fabricate a series of bolaform giant surfactants with branched architecture. By tuning the volume fraction and the ratio between the linking chain and side chain, various phases have been identified, including three-phase-four-layer lamellae, graphene-like honeycombs, tetragonally packed cylinders, and two-phase lamellae. Notably, the lattice dimension of obtained columnar structures is ∼12 nm, corresponding to sub-10 nm cylinder diameters. As revealed by temperature-dependent small-angle X-ray scattering profiles, a branched architecture significantly decreases the order-disorder transition temperature by ∼90 °C. We also use semi-quantitative calculations to analyze the thermodynamic properties of the observed phases and build rational connections between phase behaviors and the corresponding branching ratios. This study shed light on fine-tuning the macromolecular assembly via molecular topology engineering.