The S1 and T1 geometries were optimized at the TDA-DFT-M062X/6-31G(d,p) level. TCzPhCor exhibits a relatively larger geometry relaxation, where the root-mean-square displacement (RMSD) value, calculated using the VMD program, 62 is 0.60 Å between S0 and S1 compared to that of TDMACPhCor (0.48 Å) and TPXZPhCor (0.48 Å) (Figure ). While TDMACPhCor shows a quite large RMSD value of 0.92 Å between S0 and T1, TCzPhCor and TPXZPhCor possess the same value of 0.77 Å. The bowl depth of corannulene in both the S1 (bowl depth = ~0.68 Å) and T1 (bowl depth = ~0.63 Å) geometries decreases by more than 15% compared to that in the S0 geometry (bowl depth = ~0.82 Å) for all three compounds (Figures and). At the relaxed S1 geometry, there is a much larger S1-T1 spin-orbit coupling (SOC) matrix element (0.40 cm -1 ) in TPXZPhCor than that in both TCzPhCor (0.10 cm -1 ) and TDMACPhCor (0.08 cm -1 ) (Figures and), while larger SOC values of greater than 0.56 cm -1 are noted from S1 to T3 (Figure ). The density of triplet states and the SOC between these and S1 should favor ISC, which should be beneficial for producing triplet excitons for RTP. At the optimized T1 geometry (Figure ), TCzPhCor, TDMACPhCor, and TPXZPhCor possess similar T1 energies (Figure ), which indicate the same LE character of the T1 state on the corannulene core (Figure ). The relatively stabilized T1 energy (Figure ) of TDMACPhCor probably originates from an LE state that extends onto the phenylene rings, which is possible due to the smaller dihedral angles between the corannulene and the p-linker than exists in TCzPhCor and TPXZPhCor (Figure ).