The synthetic approach to supramolecular systems containing one or more metallocyclam subunits is reviewed. In particular, the template synthesis of azacyclam complexes has been used to design supramolecular coordination compounds displaying multi-electron redox activity. Moreover, it is shown that whenever the supramolecular design requires a component able to provide a fast and reversible redox change, a metallocyclam subunit should be used. Finally, the design of supramolecular systems in which a light-emitting fragment (anthracene) has been linked to a metallocyclam subunit has been considered. In particular, anthracene fluorescence can be switched on/off through the CuI/CuII redox couple inside a tetra-thia-macrocyclic environment, via an electron transfer mechanism.
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