Nonaqueous Emulsion Polycondensation Enabled by a Self‐Assembled Cage‐like Surfactant

Nonaqueous emulsions are crucial for a range of applications based on water‐sensitive systems such as controlled polymerizations requiring anhydrous reaction conditions and the stabilization of readily hydrolyzable reagents or pharmacologically active components. However, defined molecular surfactants to stabilize such nonaqueous emulsions are scarce. We introduce a self‐assembled coordination cage, decorated with cholesterol functionalities, to serve as a molecular surfactant for various oil‐in‐oil emulsions of immiscible organic solvents. While the positively charged cage forms the amphiphile's polar moiety, the non‐polar cholesterol appendices can bend in a common direction to stabilize the emulsion. Templated by the droplets, polycondensation reactions were carried out to produce microstructured polyurethane and polyurea materials of different particle sizes and morphologies. Further, the amphiphilic cage can encapsulate a guest molecule and the resulting host‐guest assembly was also examined as a surfactant. In addition, the aggregation behavior of the amphiphilic cage in an aqueous medium was examined.