Fine‐Tuning of Properties of Bismacrocyclic Dinuclear Cyclidene Receptors by N‐Methylation

Abstract N ‐Methylated bismacrocyclic Cu and Ni complexes were synthesised and structurally characterised in the solid state. Their properties in solution were analysed by using NMR and ESR spectroscopies and electrochemical methods. Face‐to‐face biscyclidenes linked through polymethylene chains form rectangular boxlike cations. These moieties can host some small guest molecules (water, π‐electron donating compounds) and are stabilised by a shell of neighbouring counterions. For the bismacrocyclic dinuclear complexes containing two nickel or two copper ions, the intramolecular interactions between the metallic centres are strengthened through methylation of the macrocyclic components, as compared with the nonmethylated species. We report the electron coupling created by two unpaired electrons coming from two copper centres observed by ESR spectroscopy. Methylation weakens the electron‐acceptor properties of the complexes, which leads to less effective binding of the π‐electron‐donating guests. It also increases the stability of the lower oxidation states. In the case of the copper complexes, both Cu II /Cu I and Cu II /Cu III reversible one‐electron transfers are seen in the voltammograms. These changes in properties are interpreted as the consequences of steric repulsion between the methyl substituents and the macrocyclic ring.