Red to near-infrared phosphorescent Ir( iii ) complexes with electron-rich chelating ligands

(L^X) structure type is among the most widely studied and technologically successful classes of molecular phosphors, particularly when L^X = acetylacetonate (acac). In our work we have pioneered the use of electron-rich, nitrogen containing ancillary (L^X) ligands as a means of controlling the excited-state dynamics and optimizing them to give record-breaking phosphorescence quantum yields. This paper progresses through our work in three distinct regions of the spectrum - red, deep-red, and near-infrared - and summarizes the many insights we have gained on the relationships between molecular structure, frontier orbital energies, and excited-state dynamics.