“…Due to their drug-like properties, their good solubility, lipophilicity, metabolic stability, and bioavailability, sophisticated macrocycles were shown to possess high therapeutic potential. ,, Along this line, multidentate macrocycles are predominantly used as chelating ligands in transition metal complexes, which in turn find main application in the fields of biomedical imaging, biomimetics, and catalysis. , Here, in particular, tetradentate N-macrocyclic systems, with the 14-membered ring cyclam 1 (=1,4,8,11-tetraazacyclotetradecane) as one of the most common representatives, proved to be versatile applicable (Figure ). − While the nickel complex [Ni(cyclam)] 2+ 2 with the tetraaza ligand 1 is known as an efficient and selective electrocatalyst for the reduction of CO 2 to CO, the iron complex [Fe(TMC)] 2+ 3 (TMC = 1,4,8,11-tetramethylcyclam) comprising a fully methylated version of the macrocycle 1 is known for the activation of O 2 (Figure ). , In these systems, the macrocyclic ligand is the crucial component as it stabilizes the unusual intermediate Ni I and Fe IV oxidation states. − …”