The growing demand for advanced photonic and electro-optical devices necessitates the rational design of novel functional materials. Liquid crystals (LCs) are particularly promising due to their highly tunable electro-optical properties. Building on this potential, we synthesized a series of polar bent-core LCs, F4-na (dipole moment ~9.4D), featuring a tetrafluorinated terminal motif and varying terminal chains. Distinct structure-property relationships are observed in this series of compounds, with the shorter chain homologues forming polar cybotactic clusters (Ncyb phase) alongside nematic and tilted smectic phases. Dielectric spectroscopy reveals non-trivial dipolar ordering, attributed to short-range polar order within cybotactic clusters, notably present without net macroscopic polarization. Under an AC field, the materials form electroconvection patterns, suggesting potential for optical modulation devices. Furthermore, the F4-na materials, particularly the lower homologues showing cybotactic clusters, stabilize the otherwise unstable Blue Phase (BP) at room temperature when doped with a chiral additive, achieving a maximum BP range of 22.9 °C. This overcomes the challenges in achieving room-temperature BP with our easily synthesizable materials, holding strong potential for 3D photonic applications. Overall, our findings offer promising opportunities for advancing room-temperature photonic and electro-optical devices while enhancing the understanding of self-assembly in soft functional materials.
