Design of liquid crystals with 'de Vries-like' properties: structural variants of carbosilane-terminated 5-phenylpyrimidine mesogens.

Structural variants of the 'de Vries-like' mesogen 5-[4-(12,12,14,14,16,16-hexamethyl-12,14,16-trisilaheptadecyloxy)phenyl]-2-hexyloxypyrimidine (QL16-6), including two isomers with branched iso-tricarbosilane end-groups, were synthesized and their mesomorphic and 'de Vries-like' properties were characterized by polarized optical microscopy, differential scanning calorimetry, small angle and 2D X-ray scattering techniques. A comparative analysis of isomers with linear and branched tricarbosilane end-groups shows that they exhibit comparable mesomorphic and 'de Vries-like' properties. Furthermore, the difference in effective molecular length L _eff between the linear and branched isomers in the SmA and SmC phases (ca. 4-5 Å), which was derived from 2D X-ray scattering experiments, suggests that the linear tricarbosilane end-group is hemispherical in shape on the time-average, as predicted by a DFT conformational analysis at the B3LYP/6-31G* level.