Novel 2-(4-octylphenyl)pyridin-5-yl alkanoates and alkenoates: Influence of dipoles and chain conformation on smectic C formation

A series of 2-(4-octylphenyl)pyridin-5-yl alkanoates has been synthesized and found to exhibit smectic mesomorphism including the smectic C phase. The influence on the transition temperatures of introducing a carbon-carbon double bond in the terminal alkanoyloxy (ester) chain of the alkanoates to produce the corresponding alkenoates has also been investigated. The position and configuration of the double bond has been changed systematically in order to determine the optimal configuration and conformation of the terminal chains for smectic C formation. The observed results are consistent with a linearly-extended (alternately cis and trans) conformation of the chain. The dependence of the transition temperatures on chain length was studied for one homologous series each of the alkanoates and the (E)-alk-2-enoates. The new esters are constitutional isomers of the 5-(4-octylphenyl)pyridin-2-yl alkanoates and alkenoates previously synthesized (differing only in the position of the nitrogen atom). Comparisons revealed consistently higher smectic C transition temperatures and lower ordered smectic tendencies for the new esters. The dependence of S-C formation on the position and number of dipoles associated with oxygen atoms, nitrogen atoms and carboxy groups was also investigated. Several of the new esters exhibit remarkably low viscosity values (i.e. short response times) in an optically active base mixture used for evaluation and comparison purposes.