AbstractThe synthesis, characterization and evaluation in solid-state devices of a series of 8 cationic iridium complexes bearing different numbers of methoxy groups on the cyclometallating ligands are reported. The optoelectronic characterization showed a dramatic red shift in the absorption and the emission and a reduction of the electrochemical gap of the complexes when a methoxy group was introduced para to the Ir-C bond. The addition of a second or third methoxy group did not lead to a significant further red shift in these spectra. Emission maxima over the series ranged from 595 to 730 nm. All complexes possessing a motif with a methoxy group at the 3-position of the cyclometalating ligands showed very short emission lifetimes and poor photoluminescence quantum yields whereas complexes having a methoxy group at the 4-position were slightly blue shifted compared to the unsubstituted parent complexes, resulting from the inductively electron withdrawing nature of this directing group on the Ir-C bond. Light-emitting electrochemical cells were fabricated and evaluated. These deep red emitters generally showed poor performance with electroluminescence mirroring photoluminescence. DFT calculations accurately modelled the observed photophysical and electrochemical behavior of the complexes and point to an emission from a mixed charge transfer state.