The molecular constituents and the molecular complex studied in the present work are depicted in Figure (a) and (b). Panel (c) of Figure shows the electronic density of states projected onto each molecular entity. The calculated HOMO level of an isolated CN6-CP molecule and that of a p(g 4 2T-TT) oligomer are at -10.44 eV and -6.22 eV, respectively, with the latter being significantly higher than the former, such that p-type doping is efficiently driven in this system, and even double doping is possible as discussed in the following. In this context, it is important to note that absolute values of orbital energies strongly depend on the DFT functional used, only relative ordering and changes are relevant for the discussions in the present work. For the CN6-CP:2p(g 4 2T-TT) complex, as shown by the molecular orbitals in Figure (b) and the projected density of states in Figure (c), both α and β HOMO are located on the dopant while one LUMO is located on oligomer I and the other is located on oligomer II. The spatial relocation of HOMO electrons to the CN6-CP site in the complex already indicates double doping. To quantify the amount of charge transferred, we also calculate the Hirshfeld charges of each molecular entity in the complex. With a charge of -1.73e on the CN6-CP it is evident that di-anion formation has occured as the result of an integer charge transfer of two electrons. The OSC I and OSC II oligomers are charged with +0.96e and +0.77e, respectively. This, together with the HOMOs residing on the dopant, clearly evidences double doping where each oligomer donates one electron to the CN6-CP molecule, giving rise to di-anion dopant formation. The molecular states corresponding to the two doping induced polarons in the doubly doped complex are close in energy both located at about -2.65 eV, cf. Figure ). These two polaron states show a certain spatial shift to opposite directions along the conjugated chains, cf. Figure . This behavior is different from that of an isolated polaron and manifests the repulsive interaction between the two polarons with equal charge. We note that in these calculations we did not find the formation of a bi-polaron or side-by-side polaron state on a single polymer chain.