shows a doubly degenerate HOMO within the ε N range considered, while the roles of LUMO and LUMO+1 are reversed when increasing the electron-withdrawing character of the aza N atoms. In the case of PLY-6N, for increasingly negative ε N values we have a change in the nature of HOMO and HOMO-1 as well as LUMO and LUMO+1. For comparison, the HF-MOs relevant to PLY are provided in SI Section S3. Unlike PLY-3N and PLY-6N, PLY exhibits energy levels that are symmetrically distributed above and below the SOMO. The varying |⟨ D⟩| and oscillator strength behavior observed for PLY-3N and PLY-6N with changes in the aza nitrogen PPP site energy underscores the crucial role played by heteroatoms on the phenalenyl rim in breaking the particle-hole symmetry. Figure illustrates |⟨ D⟩| and the oscillator strength dependence on the phenalenyl rim parameters, specifically ε N and U N . The green dot on the maps corresponds to the PLY parameters, where the rim is only composed of carbon atoms. If starting from this point we start decorating sites 2, 6, and 10 (cf. Fig. ) with electron-withdrawing atoms, with progressively more negative on-site energy, the particle-hole symmetry breaking is strengthened as shown by increasingly larger values of the average difference operator. As a result, the color map on the right also shows an increasing oscillator strength for the 2 E ′′ ← 2 A ′′ 1 transition. However, upon increasing the on-site electron repulsion on sites 2, 6, and 10 from the value relevant to carbon atoms to that relevant to nitrogen atoms, the entity of the particle-hole symmetry breaking gets reduced. The red dot on the map corresponds to the parameters relevant to PLY-3N. For the sake of completeness, corresponding color maps obtained decorating sites 1, 3, 5, 7, 9, and 11 (cf. Fig. ) with electron-withdrawing atoms are reported in the SI Section S8 and show a similar behavior.