In this work, we report our latest results regarding the self-assembly properties of two Ru-acetylides complexes and their corresponding free organic ligands, in solution and in the solid state. The four compounds show mesogenic properties, which we have rationalized thanks to extensive DSC, SAXS, POM, FTIR and molecular dynamic investigations. We clearly establish that hydrogen bonds stabilize the supramolecular structures, and that introducing the metal center and its coordination sphere induces large change in the liquid crystal properties. In addition, for the monoacetylide compound Ru-2, solution-state studies helped us rationalize its supramolecular abilities. In particular, we demonstrate that Ru-2 follows an isodesmic growth supramolecular polymerization in aromatic solvent.