Liquid-crystalline mesogens based on cyclo[6]aramides: distinctive phase transitions in response to macrocyclic host-guest interactions.

Producing macrocyclic mesogens that are responsive to guest encapsulation presents a significant challenge. Cyclo[6]aramides, a type of macrocycle with a hydrogen-bond-constrained backbone, exhibit thermotropic lamellar, discotic nematic, hexagonal, and rectangular columnar mesophases over a considerably wide temperature range, including at room temperature. Additionally, cyclo[6]aramides show unusual mesophase transitions from lamellar to hexagonal columnar phase mediated by macrocyclic host-guest (H-G) interactions between the macrocycles and alkylammonium salts. The phase transition, triggered by an organic guest engaging in H-G interactions with a macrocyclic cavity, provides a novel strategy for manipulating the properties of liquid-crystalline materials. The crystal structure of a homologous cyclo[6]aramide reveals a disk-shaped, near-planar molecular backbone that facilitates intermolecular π-π stacking and leads to columnar assembly.