Two mesogenic homologous series involving ester-azo central linkages with a biphenyl moiety have been synthesized, such as 4′-[(4-n-alkoxyphenyl) diazenyl] biphenyl-4-ol (series I) and 4′-[(4-n-alkoxyphenyl) diazenyl]-4-butoxy phenyl biphenyl-4-carboxylate (series II). Azobiphenyl of series I having a free hydroxyl group with strong hydrogen bonding exhibits a high-temperature enantiotropic smectic phase. Whereas in series II, ...