The energies of the frontier molecular orbitals (FMOs) were inferred from the electrochemical behavior of TCzPhCor, TDMACPhCor, and TPXZPhCor using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in degassed dichloromethane (DCM), with tetra-nbutylammonium hexafluorophosphate, [ n Bu4N]PF6, as the supporting electrolyte (Figure ). The oxidation potentials (Eox), determined from the DPV peak values, are 1.29 V (TCzPhCor), 0.81 V (TDMACPhCor), and 0.73 V (TPXZPhCor) versus SCE. The corresponding HOMO energies are -5.64 eV, -5.13 eV, and -5.07 eV for TCzPhCor, TDMACPhCor, and TPXZPhCor, respectively, consistent with the trend in calculated HOMO energies (Figure ) and reflecting the increasing strength of the donor across the series. TDMACPhCor and TCzPhCor have similar Ered of -2.02 and -1.94 V, respectively, which align well with their similar LUMO energies (Figure ). However, the Ered of TPXZPhCor (-1.78 V) is anodically shifted, in line with the DFT prediction, which we ascribe to a more delocalized electronic distribution of the LUMO on the corannulene and the phenylene linker. ), originating from the LE p-p * transitions on the corannulene core. A weak CT transition band at around 400 nm is observed in TDMACPhCor and TPXZPhCor (Figure ). The enhanced molar absorptivity coefficients of the band at about 300 nm, for all three compounds compared to both TPhCor and corannulene, are the result of contributions from LE transitions on the donors (Figures ). The optical bandgaps, calculated from the intersection point of the normalized absorption and emission spectra, for TCzPhCor, TDMACPhCor, and TPXZPhCor are 3.04 eV, 3.01 eV, 2.90 eV, respectively (Figure ).