The amphoteric 5-(4-cyanophenyl)dipyrrin ligand, offering three distinct states, i.e., cationic, neutral, and anionic, has been exploited for the formation of a 1-D hydrogen-bonded network in its protonated form and both homo- and heterobinuclear metallamacrocycles, in its neutral and deprotonated states, respectively, with a variety of coordination modes.