The solvatochromic study reveals only a minimal change in λPL with respect to solvent polarity for both complexes (Figure ), indicating that despite the unstructured emission, the excited state has predominantly LC character. Indeed, there is effectively little change in the emission onsets of the PL spectra at room temperature and at 77 K, which is also consistent with the emission originating from an LC state. The emission of Ir(dFppy)2(pmi) decays with monoexponential kinetics, with a photoluminescence lifetime, tPL, in MeCN of 802 ns, shorter than the previously reported value from Li et al. (1.8 µs in DCM). 15 Ir(dFppy)2(iCzmi) was found to decay with biexponential kinetics (τPL1 = 729 ns (43%) and τPL2 = 2.9 µs (57%) in MeCN). Such biexponential decay behavior is not unprecedented for heteroleptic Ir(III) complexes. The increase in τPL from Ir(dFppy)2(pmi) to Ir(dFppy)2(iCzmi) is likely attributed to the increased 3 LC character in Ir(dFppy)2(iCzmi), and thus the smaller degree of spin-orbit coupling for the T1-S0 transition. Both complexes have very short τPL in air of around 25 ns (Table ), showcasing significant quenching of the triplet excited state by O2. The corresponding estimated radiative (kr) and non-radiative (knr) decay rate constants (Table ) reveal a significantly faster kr for Ir(dFppy)2(pmi) compared to Ir(dFppy)2(iCzmi), while their knr are reasonably similar.