As outlined in Section 1, commonly used all-electron methods for organic radicals underscore the critical importance of accurately representing the potentially strong multiconfigurational nature of electronic states in these compounds. However, the rapid growth in the number of multiple excited configurations makes higher-order studies with all-electron methods impractical for large systems. In contrast, the PPP model, with its minimal active space, is particularly well-suited for examining the role of higher-order excited configurations in organic radicals. It is important to exercise caution when extending pure spin excited state theories from closed-shell systems to radicals, as the definition of excitation levels needs to be re-evaluated. Specifically, single excitations must be expanded to include double excitations which involve the simultaneous promotion of an α electron from the SOMO to virtual MOs and the promotion of a β electron from occupied MOs to the SOMO. This leads to the spin pure extended CIS (XCIS) theory for the excited states of radicals. The extension to higher order excitations leads to XCISD, XCISDT, etc. In the following we will always , and no effect of particle-hole symmetry breaking is expected. In panel b, the three aza nitrogens on the molecular rim stabilize the 2 A ′′ 2 dark state by ∼0.5 eV with respect to PLY. This effect is not observed for the 2 E ′′ doublet, which, however, gains oscillator strength due to partial particle-hole symmetry breaking induced by doping with three nitrogen atoms on the molecular rim (as discussed below). In panel c, the six nitrogens stabilize the 2 A ′′ 2 dark state so much that it ends up below the doubly degenerate state, which remains almost at the same energy as in PLY and PLY-3N. In both PLY-3N and PLY-6N, the nitrogen atoms located on the rim play a more significant role in breaking particle-hole symmetry compared to the minor PPP on-site energy variations induced by inductive effects. Finally, in all three cases the first excited quartet state 4 A ′ 1 is always well above both 2 E ′′ and 2 A ′′ 2 doublet excited states, being not appreciably affected by the increasing number of aza nitrogen atoms on the molecular rim.