2.2.2. DFT Calculations. Both DFT and time-dependent (TD)-DFT calculations using the Gaussian program were employed to elucidate the electronic structures of these products. In these calculations, the structures of 2-4 obtained from SCXRD data (see Sec. 2.3) were used as the initial models, while TBBT was modeled using methanethiolate (C1) to reduce the calculation cost (Figure ). No changes were made to the TDT moiety of 3 nor PDT moiety of 4 (Figure ). Figures 2 and S11 presents the predicted orbitals and simulated absorption spectra of [Au24Pt(C1)18] 0 (2'), [Au24Pt(C1)12(TDT)3] 0 (3'), and [Au24Pt(C1)12(PDT)3] 0 (4') (Table ). Consistent with the experimental spectra (Figure ), the absorption intensity increased as the energy increased. The absorption spectra and orbitals of 2' resembled those of [Au24Pt(C1)18] 0 , which were previously reported. Each of these three NCs had six valence electrons with LUMO, HOMO, and HOMO-1 frontier orbitals containing superatomic P and D orbital shapes (Figure ). The predicted shapes of these orbitals, especially the characteristic superatomic orbitals distributed inside the Au12Pt cores, were similar for all three NCs. However, 3' and 4' had long chain-like staple morphologies connected by TDT or PDT moieties, which formed networks, leading to highly symmetric structures belonging to the D3 point group (Scheme 1). For this reason, both NCs exhibited significant orbital degeneracy (Figure ).