Shape‐Changing Multiphase Microparticles from Complex Liquid Crystal Emulsions

ABSTRACT Complex multiphase emulsions containing liquid crystals (LCs) offer precise morphological control and dynamic tunability, enabling applications in optics, sensing, and soft matter. Here, we report a simple and scalable bulk‐emulsification strategy that circumvents the reliance on microfluidic fabrication to produce liquid crystalline network (LCN) microparticles spanning single, double (Janus), and triple emulsion morphologies within a genuinely colloidal size regime (10–20 µm). By adjusting crosslinking density and interfacial conditions, we program the LC alignment within the droplets, thereby dictating the mode and direction of actuation after photopolymerization. Single emulsions, Janus particles—coupling an active LCN hemisphere to a passive PDMS compartment—and, for the first time, triple LC emulsions—incorporating a third immiscible phase (a fluorinated oil)—are obtained via this straightforward and scalable approach. Across all morphologies, the particles exhibit robust, reversible, large‐amplitude deformations under heating, as well as chemoresponsivity through anisotropic swelling in organic solvents. In addition, the Janus particles exhibit gravitational self‐orientation, while the triple LC emulsions retain their multiphase architecture and display tunable geometries. As a proof of concept, these responsive behaviors are exploited to realize adaptive microlenses with thermally tunable focal plane and magnification, establishing complex LC emulsions as a scalable platform for multifunctional microactuators.