We synthesised a series of dissymmetric bistolane derivatives and evaluated their liquid-crystalline (LC) and photoluminescence properties in detail. In measuring LC behaviours, rational structural design based on the dissymmetric molecular structure and electron-density distribution facilitated the production of the LC phase with a wide temperature range (up to 97 °C). In addition, dissymmetric bistolane derivatives were shown to strongly emit blue-photoluminescence in dilute solution and in crystalline states. It was found that dissymmetric bistolanes possess emissive features in even the LC phase and photoluminescence behaviours such as emission intensity and colour were sensitively switched depending on the molecular aggregate structure caused by applying a thermal stimulus.

We herein describe the synthesis of novel pentafluorinated tolane fluorophores, which possess an extended π-conjugated structure with a large molecular dipole moment along the longitudinal axis. We also report a detailed evaluation of both the photophysical and thermal behaviors of these fluorophores. All molecules displayed photoluminescence (PL) characteristics in both the crystalline state and in dilute solutions. The large longitudinal dipole moment induced solvatochromic PL behavior, which switched sensitively with changes in the solvent polarity. In addition, incorporation of the fluorinated tolane-based solid-state light-emitting moiety into the polymer side chain was found to be responsible for the PL characteristics observed in the solid state. It was also noteworthy that the polymerization protocol led to a significant enhancement in the thermal stability, with the thermal decomposition temperature increased by 90 °C. Accordingly, novel solid-state light-emitting materials with high thermal stabilities were successfully developed as promising candidates for use in light-emitting and optoelectronic applications.

In this study, we designed and synthesized novel pentafluorinated bistolane derivatives with 2-chloropentyl or 2-chlorohexyl flexible units as novel light-emitting liquid crystals (LELCs). By measuring the phase-transition behaviors, all derivatives were found to display liquid-crystalline (LC) phases during both heating and cooling processes. Among the novel bistolanes, the S- and R-configured derivatives exhibited a chiral nematic (N*) phase with a typical Grandjean optical texture. Interestingly, the chiral derivatives also exhibited a blue phase with a typical platelet texture in a narrow temperature range (2–4 °C). Photophysical measurements revealed that the 2-chloroalkoxy-substituted pentafluorinated bistolanes exhibited intense photoluminescence (PL) both in solution and in crystalline phases. The PL characteristics, especially the maximum PL wavelength, were found to switch sensitively during the heating and cooling cycles depending on the molecular aggregates through the crystal (Cr) ⇄ N* phase transition. The 2-chloroalkoxy flexible units induced dynamic changes in the LC and PL properties, providing valuable insight into the potential of various LELCs as PL sensing materials.