One series of 4-n-octyl-N-(4-X-benzylidene)anilines and two series of polar orthopalladated complexes derived from these of type Pd2(μ-Y)2p-X-C6H3-CH = N-C6H4-C8H172;X: -H, -F, -Cl, -Br, -NO2, -CN, -CH3, -OCH3, -CF3, -COOCH3, -OCOCH3and -OCOQH5;Y: -OAc and -Cl; have been synthesized and their mesogenic properties studied. In the polar Schiff bases used as organic ligands, the polar end group determines both the presence of the mesophase and the type of mesophase exhibited. In the complexes, however, it is the central structure of the molecule that practically always determines mesogenic behaviour. No acetato-bridged complex is mesogenic. All the chloro-bridged complexes, however, show mesogenic behaviour. All these compounds show smectic A mesophases with the exception of the CN compound, which only exhibits a nematic mesophase.