Self‐Assembled Nanostructured Microgels with Reconfigurable Morphologies

ABSTRACT We report a new class of supramolecularly assembled complex emulsions in which nanostructured organogels derived from bent‐core amphiphiles constitute one of the internal compartments. The molecular design of these amphiphiles, combining biphenyl (Bi) or ester (B1) lateral units with tetraethylene glycol and alkyl terminal chains, promotes efficient aggregation pathways and robust gelation. The resulting organogels exhibit fibrillar, tubular, and helical networks, with several systems displaying hierarchical arrangements characteristic of helical nanofilament (HNF) organizations, thereby transcribing liquid‐crystalline order into gel phases. Emulsification of the organogels into aqueous media yields supramolecular microgels that not only preserve their internal fibrillar architectures but also retain HNF‐like order, representing the first demonstration of nanostructured microgels formed through the self‐assembly of low‐molecular‐weight amphiphiles. Beyond single microgels, we prepare complex emulsions in which an organogel phase coexists with a fluorocarbon oil. These multicompartment droplets exhibit dynamic reconfigurability, switching between organogel‐in‐fluorocarbon‐in‐water (OG/F/W), Janus, and fluorocarbon‐in‐organogel‐in‐water (F/OG/W) morphologies. The ability to couple bent‐core self‐assembly with colloidal processing into reconfigurable complex emulsions establishes nanostructured microgels as an innovative adaptive soft‐material platform with opportunities in sensing, controlled delivery, bioimaging, and photonic technologies.