Data from the Ir[tBu]-BAr F 4 complex provides the magnitude of the intramolecular dipole moment, which we use to compute absolute dipoles for each excited-state Species in table 4. We find that the dipole moment we observe for Ir[tBu]-BAr F 4 does not meet with our simplistic center-of-mass approximation, which suggests an MLCT-state dipole moment of 16.8 D. Instead, we observe a transient dipole moment of only 5.2 ± 1.6 D in the fully relaxed MLCT (Species B). This discrepancy could partly be accounted for if the ground and excited-state dipole moments oppose each other. However, even exact opposition would not make up the whole difference. We can eliminate the possibility that the small observed transient dipole moment is a more subtle manifestation of ion-pair reorganization by BAr F 4 , as the neutral homoleptic complex Ir(ppy) 3 (see SI section Non-ionic Iridium(III) Complex) displays an even smaller change in excited-state dipole moment (see Supplementary Table ). Rather, we posit that the excited-state dipole moment is intrinsically small in these complexes, consistent with the high degree of mixing between the orbitals involved. This indicates that the simplistic picture of the lowest MLCT state as an integer charge localized on the bpy ligand is incorrect for this complex, and is likely similar in other related Ir(III) photoredox catalysts.