Metallosupramolecular systems heavily rely on the correct choice of ligands to obtain materials with desired properties. Engaging this problem, we present three ligand systems and six of their mono- and dinuclear complexes, based on the subcomponent self-assembly approach using electron-deficient pyridylcarbaldehyde building blocks. The properties are examined in solution by NMR and UV-vis spectroscopy and CV measurements as well as in solid state by single crystal X-ray diffraction analysis. Ultimately, the choice of ligands allows for fine-tuning of the electronic properties of the metal centers, complex-to-complex transformations, as well as establishing distinct anion-π-interaction motifs.