Rational Design of Rod‐Like Liquid Crystals Exhibiting Two Nematic Phases

Recently, a polar, rod-like liquid-crystalline material was reported to exhibit two distinct nematic mesophases (termed N and NX ) separated by a weakly first-order transition. Herein, we present our initial studies into the structure-property relationships that underpin the occurrence of the lower-temperature nematic phase, and report several new materials that exhibit this same transformation. We have prepared material with significantly enhanced temperature ranges, allowing us to perform a detailed study of both the upper- and lower-temperature nematic phases by using small-angle X-ray scattering. We observed a continuous change in d spacing rather than a sharp change at the phase transition, a result consistent with a transition between two nematic phases, structures of which are presumably degenerate.