DFT and TD-DFT calculations were performed to gain insight into the ground-and excited-state electronic properties of Ir(dFppy)2(pmi) and Ir(dFppy)2(iCzmi) (Figure ). The two complexes show reasonably different electronic density distributions, with the LUMO, localized primarily on one of the dFppy ligands for Ir(dFppy)2(pmi), while for Ir(dFppy)2(iCzmi), the LUMO density is distributed across both dFppy ligands and also across the iCz portion of the ancillary ligand, accounting for the slight LUMO stabilization of 0.15 eV. The HOMO for Ir(dFppy)2(pmi) is distributed between the metal center and the difluorophenyl and phenyl moieties the dFppy and pmi ligands, respectively. This is typical of Ir(III) complexes of the type Ir(C^N)3 and Ir(C^N)2(L^L). By contrast, the HOMO of Ir(dFppy)2(iCzmi) is localized on both the Ir center and almost entirely on the electron-rich iCzmi ligand, which consequently leads to a destabilization of the HOMO of Ir(dFppy)2(iCzmi) of 0.13 eV compared to Ir(dFppy)2(pmi). The simultaneous LUMO stabilization and HOMO destabilization of Ir(dFppy)2(iCzmi) with respect to Ir(dFppy)2(pmi) culminates in a very similar HOMO-LUMO gap for each complex at 3.41 and 3.38 eV for Ir(dFppy)2(iCzmi) and Ir(dFppy)2(pmi), respectively (Figure ). It follows that both complexes possess reasonably similar predicted S1 and T1 energies, though those of Ir(dFppy)2(iCzmi) are slightly lower in energy. The singlet-triplet energy gap (ΔEST) for both complexes is also relatively small at 0.25 and 0.26 eV, respectively. The spin density distribution plots of both complexes are shown in Figure . The spin density of the T1 state of Ir(dFppy)2(pmi) is distributed across the metal centre, one of the dFppy ligands and the phenyl portion of the pmi ligand, suggesting an excited state of mixed 3 CT/ 3 LC character. For Ir(dFppy)2(iCzmi), the majority of the T1 spin density is localised much more on the metal centre, indicaTng a mixture of 3 MLCT and 3 LC character. Similar T1 energies of 2.84 and 2.80 eV were predicted for Ir(dFppy)2(pmi) and Ir(dFppy)2(iCzmi), respectively. and Ir(dFppy) 2 with orbital density plots of the HOMO and LUMO of both complexes. b) Triplet spin density distribuIons of Ir(dFppy) 2 (pmi) and c) Ir(dFppy) 2 (iCzmi) (isovalue of 0.02).