Nanocompartmentalization of soft materials with three mutually immiscible solvents: Synthesis and self-assembly of three-arm star-polyphiles

We report synthesis, thermotropic, and lyotropic mesomorphism of a family of novel "star-polyphiles": small star-shaped molecules bearing three mutually immiscible arms, hydrophilic (oligoethylene glycol), oleophilic (alkanes), and fluorophilic (perfluorinated alkanes), attached to a central 1,3,5-trihydroxybenzene core. A facile, flexible multistep synthesis giving high-purity yields of 14 distinct members of the family is described, with variable arm lengths, forming crystalline, or various mesostructured gel phases in their neat state at room temperature. Furthermore, we show that specific members of these star-polyphiles can be simultaneously loaded with up to three mutually immiscible solvents, dodecane, perfluoro-nonane, and water, to form liquid crystals and microemulsions with multiple chemically distinct mesoscale compartments. The mesoscale chemical polyfunctionality of these polyphiles, coupled with thermotropic and lyotropic polymorphism, make them promising potential soft materials for a variety of applications, including host matrices for multiple mutually immiscible chemicals and drug delivery.