The nematic-to-isotropic, crystal-to-nematic, and supercooled liquid-to-glass temperatures are studied in the liquid crystal 4-pentyl-4'-cyanobiphenyl (5CB) confined in self-ordered nanoporous alumina. The nematic-to-isotropic and the crystal-to-nematic transition temperatures are reduced linearly with the inverse pore diameter. The finding that the crystalline phase is completely suppressed in pores having diameters of 35 nm and below yields an estimate of the critical nucleus size. The liquid-to-glass temperature is reduced in confinement as anticipated by the model of rotational diffusion within a cavity. These results provide the pertinent phase diagram for a confined liquid crystal and are of technological relevance for the design of liquid crystal-based devices with tunable optical, thermal, and dielectric properties.

Hexa‐peri‐hexabenzocoronene derivatives show a record high negative volumetric thermal expansion coefficient within the crystalline phase. Responsible for the negative thermal expansion is the increase of the tilt angle and the improved packing of the discotic cores with temperature and this has implications in the design of organic electronic devices as well as in advanced nanocomposites with controlled thermal properties.

The role of alkyl chain substitution on the phase formation and core dynamics is studied in a series of diphenylamine functionalized perylenemonoimides (PMIs), by X-ray scattering, calorimetry and site-specific solid-state NMR techniques. In addition, the strong dipole associated with the donor-acceptor character of the molecules allow an investigation of the dynamics with dielectric spectroscopy. The self-assembly revealed an ordered phase only in PMIs with branched alkyl chains. This phase comprises a helical stacking of molecules with a molecular twist angle of 60 degrees. Results from solid-state NMR further pointed out the importance of intramolecular hydrogen bonding in stabilizing the intracolumnar packing within the ordered phase. Moreover, the core dynamics are frozen as revealed by the value of the dynamic order parameters and the reduced strength of dipolar relaxation. The kinetics of phase transformation from the isotropic to the ordered phase proceeds via a nucleation and growth mechanism, and the rates are dominated by the nucleation barrier. Within the isotropic phase the core dynamics display strong temperature dependence with rates that depend on the number of methylene units in the alkyl chains.