Liquid-crystalline (LC) physical gels are a new class of dynamically functional materials consisting of liquid crystals and fibrous aggregates of molecules that are called "gelators". Liquid-crystalline physical gels, which are macroscopically soft solids, exhibit induced or enhanced electro-optical, photochemical, electronic properties due to the combination of two components that form phase-separated structures. In this tutorial review, we describe the materials design and structure-property relationships of the LC physical gels. The introduction of self-assembled fibers into nematic liquid crystals leads to faster responses in twisted nematic (TN) mode and high contrast switching in light scattering mode. Furthermore, the LC physical gels can be exploited as a new type of materials for electro-optical memory. This function is achieved by the control of reversible aggregation processes of gelators under electric fields in nematic liquid crystals. Electronic properties such as hole mobilities are improved by the introduction of fibrous aggregates into triphenylene-based columnar liquid crystals. The incorporation of photochromic azobenzenes or electroactive tetrathiafulvalenes into the chemical structures of gelators leads to the preparation of ordered functional materials.

Liquid-crystalline macrocyclic compounds, tethered by two or three azobenzenes bearing alkoxy side chains, exhibit isothermal phase transitions from liquid-crystal to isotropic as well as from crystal to isotropic phases upon light irradiation due to the drastic conformational change of their macrocyclic backbone.

Photoinduced phase transitions caused by photochromic reactions bring about a change in the state of matter at constant temperature. Herein, we report the photoinduced phase transitions of crystals of a photoresponsive macrocyclic compound bearing two azobenzene groups (1) at room temperature on irradiation with UV (365 nm) and visible (436 nm) light. The trans/trans isomer undergoes photoinduced phase transitions (crystal–isotropic phase–crystal) on UV light irradiation. The photochemically generated crystal exhibited reversible phase transitions between the crystal and the mesophase on UV and visible light irradiation. The molecular order of the randomly oriented crystals could be increased by irradiating with linearly polarized visible light, and the value of the order parameter was determined to be −0.84. Heating enhances the thermal cis‐to‐trans isomerization and subsequent cooling returned crystals of the trans/trans isomer.

Discotic liquid‐crystalline (LC) physical gels have been prepared by combining the self‐assembled fibers of a low‐molecular‐weight gelator and semiconducting LC triphenylene derivatives. The hole mobilities of the discotic LC physical gels measured by a time‐of‐flight method become higher than those of LC triphenylenes alone. The introduction of the finely dispersed networks of the gelator in the hexagonal columnar phases may affect the molecular dynamics of the liquid crystals, resulting in the enhancement of hole transporting behavior in the LC gel state.

Aligned photoluminescent fibers are formed by the self assembly of an oligo‐(p‐phenylenevinylene) derivative (OPV) in oriented liquid crystals (see figure). The aligned fibers of OPV show polarized yellow emission in the direction of the long axis of fibers. New types of electro‐optical and photonic systems can be visualized in the future as the polarized luminescence of these fibers is combined with the dynamic properties of the liquid crystals.