Metal complexes with naphthalene-diimide and perylene-diimide-based ligands: supramolecular interactions and catalytic implications

This doctoral thesis delves into the design and development of new ligand precursors and organometallic complexes through the combination of two different types of rylene-diimides (RDIs), with N-heterocyclic carbene (NHC)-based ligands. The novelty and interest of the results described in this doctoral thesis can be summarized in the following three points: • We show that imide functionalization of PDI/NDIs with NHC units can be used as a way to generate redox-switchable ligands with application in homogeneous catalysis. • We describe how the catalytic properties of a simple metal complex can be reversibly modified by using tailored-designed redox-switchable rylene-decorated NHC ligands, thus offering a new and simple approach to modulate the catalytic activity and to elucidate or review reaction mechanisms. • We describe and fully characterize a new type of (chloride)lp– π interaction between the chloride ligands of the Ir(III) complex and the heterocycles of the NDI/PDI moieties combining spectroscopic/computational determination of the lp–π interaction