Switching Chirophilic Self-assembly: From meso-structures to Conglomerates in Liquid and Liquid Crystalline Network Phases of Achiral Polycatenar Compounds

Spontaneous generation of chirality from achiral molecules is a contemporary research topic with numerous implications for technological applications and for the understanding of the development of homogeneous chirality in biosystems. Herein, a series of azobenzene based rod-like molecules with an 3,4,5-trialkylated end and a single n-alkyl chain involving 5 to 20 aliphatic carbons at the opposite end is reported. Depending on the chain length and temperature these achiral molecules self-assemble into a series of liquid and liquid crystalline (LC) helical network phases. A chiral isotropic liquid (Iso₁*^]) and a cubic triple network phase with chiral I23 lattice were found for the short chain compounds, whereas non-cubic and achiral cubic phases dominate for the long chain compounds. Among them a mesoscale conglomerate with I23 lattice, a tetragonal phase (Tet_bi) containing one chirality synchronized and one non-synchronized achiral network, an achiral double network meso-structure with Ia d space group and an achiral percolated isotropic liquid mesophase (Iso₁) were found. This sequence is attributed to an increasing strength of chirality synchronization between the networks, combined with a change of the preferred mode of chirophilic self-assembly between the networks, switching from enantiophilic to enantiophobic with decreasing chain length and lowering temperature. These nanostructured and mirror symmetry broken LC phases exist over wide temperature ranges which is of interest for potential applications in chiral and photosensitive functional materials derived from achiral compounds.