Natural transition orbital (NTO) analyses at the S0 geometry provide insight into the nature of excited-state transitions (Figure ). For TCzPhCor, the S1 state possesses a LE character mostly centered on the corannulene core. However, for TDMACPhCor and TPXZPhCor, the S1 state is of CT character, reflective of the stabilization of this state compared to the LE states in the presence of the stronger electron donors; indeed, there is a progressive, although very weak, stabilization of the S1 state from 3.77 eV in TCzPhCor to 3.76 eV in TDMACPhCor and 3.67 eV in TPXZPhCor as a result of the near orthogonal conformation of the donor groups relative to the TPhCor. The DES1T1 values also decrease progressively from 0.63 eV in TCzPhCor to 0.56 eV in TDMACPhCor and 0.47 eV in TPXZPhCor (Figure ).