This report demonstrates the interrelationships between liq. cryst. superstructure and the strength of linear chains (–V-O...V = O–)n, exhibited by vanadyl-based discotic liq. crystals. The effect of mol. superstructure was detd. by studying related compds. which due to their shapes display liq. crystal phases with specific intermol. correlations between nearest neighbors. In superstructures which do not exhibit steric interactions, the strength of assocn. in the linear chain structure was controlled by the groups bridging between the Schiff-base nitrogens. Compds. with bridging group a are monomeric, compds. with bridging group b are the strongest linear chains, and compds. with bridging group c are somewhat weaker linear chains. The relative strength of the linear chains was detd. by monitoring the V=O stretching frequency and is sensitive to mesophase superstructures which produced specific steric repulsions and/or orientational preferences. Linear chain structures also influence the nature of the mesophases and produced novel polar mesophases with high intercolumnar order yet liq.-like order within the columns. This increased intercolumnar order is ascribed to an increase in the rigidity of the linear chain which holds the mesogens in a tighter registry. [on SciFinder(R)]