Achieving Robust Cholesteric Liquid Crystal Polymer Networks with High Luminescence Dissymmetry Factor

Abstract Circularly polarized luminescence (CPL) is a key enabling technology for next-generation photonics, yet developing materials combining high stability, brightness, and dissymmetry factor (glum) remains a formidable challenge. A superior strategy involves solidifying highly-ordered emissive liquid crystals into robust polymer networks, but this process is often hindered by polymerization-induced stress that destroys the delicate chiral architecture. The design principles to overcome this “stability-performance paradox” are not well understood. Here, we establish these principles through a synergistic co-design of both monomer and network. We designed a series of emissive fluorene-based monomers and discovered that a unique combination of core planarity and segmental flexibility is essential for forming a nearly ideal helical superstructure, achieving an exceptional glum of 0.60 in the fluidic state. Critically, by employing a topologically-matched, bifunctional crosslinker that minimizes network stress, this elite performance was successfully preserved. The resulting robust polymer network exhibits a final glum of 0.54, the highest value reported to date for such systems to our knowledge. In stark contrast, a conventional tetra-functional crosslinker almost annihilated the chiroptical activity. Experimental and theoretical results reveal that success hinges on a synergistic strategy: molecules predisposed to forming low-defect assembly must be paired with polymerization chemistry minimizing network-induced stress. This rational design strategy bridges the gap between ideal fluidic systems and practical solid-state chiroptical materials, paving the way for their application in advanced technologies.