Two groups of the formulae, 4-(4′-hexyloxy) phenylazo-2-(and 3) methyl phenyl-4 ″- substituted benzoates (Ia–e and IIa–e) were prepared and investigated for their mesophase behavior. Each group consists of five derivatives that differ from each other by the terminal polar substituent X which varies between CH3O, CH3, Br, NO2, and CN. Two other isomeric groups, IIIa–e and IVa–e, that exchange the terminal substituents, X and C6H13O, were ...