A series of bromoalkyloxy-substituted terphenylenes were synthesized through a Palladium cross-coupling reaction between arylboronic acids and bromoaryl derivatives. By DSC it was observed that these intermediates show a rich thermotropism in a wide range of temperature (110-180 degrees C) and by X-ray diffraction it was determined that the liquid-crystalline nature corresponds to tilted type smectic mesophases (SmC, SmF/ SmI, and a two-dimensional ordered tilted mesophase SmX).