Cascading One-Pot Synthesis of Single-Tailed and Asymmetric Multitailed Giant Surfactants

Rapid and precise synthesis of macromolecules has been a grand challenge in polymer chemistry. In this letter, we describe a convenient, rapid, and robust strategy for a one-pot synthesis of various precisely defined giant surfactants based on polyhedral oligomeric silsesquioxane (POSS). The method combines orthogonal oxime ligation, strain-promoted azide-alkyne cycloaddition (SPAAC), and thiol-ene "click" coupling. The process is usually completed within 0.5-2 h and does not require chromatography methods for purification. With near quantitative conversion efficiency, the method yields giant surfactants with distinct topologies, including single-tailed and asymmetric, multitailed giant surfactants. Both polymer tail composition and POSS surface chemistry are controlled precisely and tuned independently, enabling the design and preparation of new classes of giant surfactants.