A series of dimetallic and monometallic Cp*Ir(III) complexes bearing naphthalene-diimide-decorated N-heterocyclic carbene/pyridine [NDI-(NHC-pyridine)] ligands were prepared characterized. The show a C,C-chelating coordination the NHC-pyridine ligand, with pyridine ring ligand bound to metal via cyclometallation rather than by its nitrogen atom, although atom could be achieved subjecting one re...