To best of our knowledge, corannulene derivatives generally exhibit convex-concave stacking or "clamshell" type packing. The picture of the packing motif observed in TPXZPhCor is slightly different. The shortest equivalent distance between adjacent TPXZPhCor molecules arranged in a concave-convex manner is 11.80 Å, which is longer than those documented in previous reports and in a concave-concave manner is 16.07 Å (Figure ). We first modelled the photophysical properties of the three compounds in the gas phase using timedependent density functional theory (TD-DFT) within the Tamm-Dancoff approximation (TDA) at the TDA-DFT-M062X/6-31G(d,p) level of theory. At the optimized S0 geometries, the bowl shape of corannulene is present in all three compounds (Figure ). The bowl depth slightly decreases as the electron-donating strength of the donors increases from 0.84 Å (TCzPhCor) to 0.83 Å (TDMACPhCor) and 0.79 Å (TPXZPhCor), all shallower than those of corannulene (0.88 Å) and TPhCor (0.84 Å). The calculated bowl depths of TPhCor and TPXZPhCor coincide well with those of the single crystal structures (Figures and). Strongly twisted D-A geometries were computed for TCzPhCor, TDMACPhCor, and TPXZPhCor (Figure ). Larger dihedral angles between the donor and the phenylene bridge exist in TDMACPhCor (from 84.9° to 94.8°) and TPXZPhCor (from 81.0° to 95.7°) compared to TCzPhCor (from 51.0° to 52.5°), while the dihedral angles between the phenylene bridge and corannulene slightly increase in TDMACPhCor (from 62.6° to 65.8°) and TPXZPhCor (from 59.3° to 79.8°) than TCzPhCor (from 53.3 to 61.3°). The S0 geometry of TPXZPhCor is similar to that found in the single crystal (Figure ), where the donor groups are highly twisted with respect to the phenylene bridge and the phenylene bridge is itself strongly twisted with respect to corannulene (Figures S34). The calculated energies of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are displayed in Figures and. As expected, the HOMO and LUMO are localized on the donors and the corannulene acceptor, respectively. The progressively destabilized HOMO reflects the increasing electron-donating strength of the donors in TCzPhCor, TDMACPhCor, and TPXZPhCor, respectively, while similar LUMO energies reveal negligible electronic coupling between the donors with the corannulene acceptor. The LUMO of TPhCor is destabilized (-0.95 eV) compared to the LUMOs of three corannulene derivatives (Figure ) as it is a smaller conjugation length.