Relationship between Molecular Association and Re-entrant Phenomena in Polar Calamitic Liquid Crystals

The relationship between molecular association and re-entrant phase behavior in polar calamitic liquid crystals has been explored in two families of materials: the 4′-alkoxy-4-cyano­biphenyls (6OCB and 8OCB) and the 4′-alkoxy-4-nitro­biphenyls. Although re-entrant nematic phase behavior has previously been observed in the phase diagram of 6OCB/8OCB, this is not observed in mixtures of the analogous nitro materials. As there is no stabilization of the smectic A phase in mixture studies, it was conjectured that the degree of association for the nitro systems is greater than that for the cyano analogues. This hypothesis was tested by using measured dielectric anisotropies and computed molecular properties to obtain a value of the Kirkwood factor, <i>g</i>, which describes the degree of association of dipoles in a liquid. These computed values of <i>g</i> confirm that the degree of association for nitro materials is greater than that for cyano and offer a useful method for quantifying molecular association in systems exhibiting a re-entrant polymorphism