Copper(II) azacyclam complexes (azacyclam = 1,3,5,8,12-pentaazacyclotetradecane) containing naphthyl or dansyl subunits can be prepared by template synthesis involving proper sulfonamide derivatives as locking fragments. The macrocyclic complexes are very poorly emissive due to the fluorescence-quenching behavior displayed by Cu²⁺ ions. However, the fluorescence can be recovered as a result of the decomposition of the complexes, which induces the release of free light-emitting subunits to the solution. This reaction takes place very slowly in neutral water but its rate is increased by the presence of sulfite. Therefore, [Cu(azacyclam)]²⁺ derivatives have been investigated as simple chemical probes for the fluorogenic detection of sulfite both on laboratory and real samples. Preliminary tests performed on samples of white wine provided sulfite concentration values that are in agreement with those obtained by a standard analytical method.

A radical anion −NO₂^.− is formed upon an electrochemically reversible one‐electron reduction of the square‐planar Ni^II complex of N‐nitrobenzylcyclam. The −NO₂^.− group goes to occupy an axial position of the metal ion, thus establishing a significant electronic interaction with the metal center. In particular, the ESR spectrum supports the occurrence of an electron transfer from −NO₂^.− to the metal, which therefore presents a significant Ni^I character. On re‐oxidation, the nitrobenzyl side chain detaches and the Ni^II complex is restored, providing an example of a fully reversible redox driven intramolecular motion.

Electron donor–acceptor (EDA) complexes are characterized by charge-transfer (CT) processes between electron-rich and electron-poor counterparts, typically resulting in a new absorption band at a higher wavelength. In this paper, we report a series of novel 2,6-di(imino)pyridine ligands with different electron-rich aromatic substituents and their 1:2 (metal/ligand) complexes with zinc(II) in which the formation of a CT species is promoted by the metal ion coordination. The absorption properties of these complexes were studied, showing the presence of a CT absorption band only in the case of aromatic substituents with donor groups. The nature of EDA interaction was confirmed by crystallographic studies, which disclose the electron-poor and electron-rich moieties involved in the CT process. These moieties mutually belong to both the ligands and are forced into a favorable spatial arrangement by the coordinative preferences of the metal ion.