(603i) Polymer-Shell Confinement for Reconfigurable Symmetry in Stabilized Blue Phase Liquid Crystals

A deep mechanistic understanding of how curvature and interfacial energetics direct the formation and stabilization of crystalline order is essential for advancing the molecular engineering of soft materials with programmable optical and mechanical properties. Here, we employ a combined experimental–computational framework to elucidate the influence of polymer confinement on the phase behavior of highly chiral blue phase (BP) liquid crystals, non-reactive anisotropic solvents that spontaneously self-organize into three-dimensional cubic lattices (BPI and BPII), distinguished by double-twist cylinders interconnected through periodic disclinations (defect lines). By incorporating UV-polymerizable mesogens into BP emulsions, we induce a phase-separated polymer network that preferentially self-assembles within the high-energy disclination regions at the BP–aqueous interface. The resulting nano-architected shell, with a thickness on the order of hundreds of nanometers, emerges through defect-guided polymer self-assembly and interfacial packing. This shell imposes spatially heterogeneous curvature and anchoring fields that synergistically modulate BP nucleation pathways, symmetry selection, and lattice coherence. Beyond stabilizing BPs at ambient and elevated conditions, the shell introduces dynamic tunability, enabling reversible crystal-to-crystal transformations under thermal and electrical stimuli. This reconfigurability yields unprecedented control over photonic band structure modulation. Collectively, our results establish a generalizable platform for the design of defect-guided, curvature-confined soft crystals with adaptive optical responses, paving the way for next-generation photonic, sensing, and optoelectronic devices.