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

Abstract

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.