Supramolecular liquid crystals in binary and ternary systems

► Two groups of pyridine-based azo-dyes were prepared with lateral methyl groups attached to different positions. ► The terminal alkoxy group in both series of compounds varies between 8, 10, 12, 14, and 16 carbons. ► Two groups of hydrogen-bonded supramolecular complexes were investigated. ► Binary phase diagrams of three-component complexes were constructed. ► The lateral methyl group does not disturb smectic arrangements either in pure pyridine-based component or the complexes.