The weakly mesomorphictrans-4-alkyloxy-4′-stilbazoles(n-OPhVPy) are readily synthesised from alkyloxyiodobenzenes and 4-vinylpyridine in a palladium-catalysed Heck reaction. While the highly symmetric palladium and platinum complexestrans-[MCl2(n-OPhVPy)2] show mesophases only at very high temperatures, the lower symmetry platinum complexestrans-[PtCl2(η2-olefin) (n-OPhVPy)] melt below 100°C. Similarly, the complexes [MCl(CO)2(n-OPhVPy)] (M = Rh, Ir) are low melting. The silver complexes [Ag(n-OPhVPy)2][X] (X = C12H25OSO3, C8H17OSO3, CF3SO3) can be obtained by direct reaction of the stilbazole with AgX. These ionic materials show a rich thermotropic polymorphism, including nematic and cubic mesophases. Some fluorinated stilbazoles have also been synthesised and complexed to silver; the mesomorphism of these complexes is also reported.