This, coupled with the stronger positive solvatochromism (Df of 2223 cm -1 for MeODPA-DiKTa 1728 cm -1 for PhDPA-DiKTa) indicates a greater admixture of LRCT character in the emissive excited state of the latter (Error! Reference source not found.3c). The optical bandgaps, calculated from the intersection point of the normalized absorption and emission spectra, for PhDPA-DiKTa and MeODPA-DiKTa are 2.16 and 2.03 eV (Figure ), which mirror the trend in the electrochemical gaps of 2.18 and 2.01 V, respectively (Figure ). The transient PL decay in both aerated and degassed toluene solutions are shown in Figure . Although there is no delayed emission observed in the degassed solution like is the case for most of the DiKTa derivatives, both the lifetime and the emission intensity slightly decrease in aerated toluene. The PL lifetime, tp, of MeODPA-DiKTa is shorter at 5.5 ns than that of PhDPA-DiKTa at 18.9 ns. The prompt fluorescence and phosphorescence spectra in 2-MeTHF glass at 77 K were used to extract the S1 and T1 energies from their respective onsets (Error! Reference source not found.3d, Table ). The S1 energies are 2.19 and 1.98 eV, and the T1 energies are 1.99 and 1.75 eV, for PhDPA-DiKTa and MeODPA-DiKTa, respectively. The corresponding ΔEST values for are 0.20 and 0.23 eV, respectively, which are similar to other DPA-decorated DiKTa/TOAT derivatives like 3DPA-DiKTa (0.22 eV) and pBDPA-TOAT (0.23 eV).