Two series of salicylaldimines have been synthesized that consist of model compounds with terminal methylenic chains and reactive compounds in which the terminal chains have been modified with acrylate groups. The dicarbonylrhodium(I) complexes of these systems were prepared by reacting the ligands with the dimer [RhCl(cod)](2) and CO. Characterization of the metal-containing acrylates by H-1 NMR spectroscopy revealed that the Rh(I) can coordinate to the terminal double bond to produce pentacoordinated complexes. Furthermore, investigation of the mesogenic properties of the complexes revealed that the bulkiness of the metallic center requires the presence of at least a three-ring aromatic core to avoid the suppression of liquid crystallinity. The study was extended to include the side-chain polymers obtained from the acrylate-functionalized Schiff bases. Chelation of the preformed polyacrylate with low percentages of Rh(I) emerged as the best strategy to prepare Rh(I)-containing polyacrylates.