The obtained results from the QTAIM analysis provide compelling support for the findings obtained from the previous analyses (Figures S4.3 and S4.4 and Tables S5.3 and S5.4). Examination of the electron density at various BCPs within the studied complexes reaffirms the nature of the non-covalent interactions established upon complexation. In addition, the positive ∇ 2 ρ(r) values derived from the QTAIM analysis further validate the noncovalent nature of the interactions observed in all the cases under study. Interestingly, the values obtained for ∇ 2 ρ(r) are consistently similar for both neutral and charged compounds; however, these values are consistently an order of magnitude lower than those observed in pure ionic compounds (Figure ). This observation suggests that the presence of HBs is influenced by the surrounding charges, and consequently the systems present a clear HB-assisted ion-pair rather than a strict-ion-pair interaction. It has been established that the charge carried within the PTCs' structure is vital, and therefore it becomes crucial to conduct an in-depth investigation of the charges associated with the monomer in its isolated state and upon complexation. Firstly, a comparative analysis of the charges between the charged monomers (Figure ) and their neutral counterparts (Table .4) was conducted. In the isolated monomers, the C1 atom, which is directly attached to nitrogen, was revealed to exhibit a significant increase in positive charge in all the cases studied, from neutral to charged monomers. In contrast, the nitrogen remains relatively unchanged in the CF 3 case and slightly more negative in the presence of CH 3 and t Bu substituents, in agreement with the electrodonating nature of those substituents. Upon complexation with the anion, visible modification is observed in the C1 atom's charge for most cases, indicating a charge transfer from the anion to C1. Consequently, the C1 atom becomes less positively charged in all cases, with a more pronounced effect observed in the scenario involving the CF 3 substituents. A similar behaviour is observed for the neutral case (Figure .3), in which C1 presents the highest charge difference between the monomer and the complex. The aforementioned variation in the charge distribution within the C1 atom can also be seen in the NBO calculations. Specifically, the charge transfer from the lone pair (LP(X -)) of the anion to the antibonding orbital of the N-C bond (BD * (NC)) highlights this distinction (Table ). Nevertheless, it is important to emphasise that the magnitude of this charge transfer is significantly low when compared to the corre-sponding value associated with the HB, (Figure , light grey, Table ). Specifically, the highest value obtained for E(2) BD ( N -C) is 6.5 kJ/mol, while E(2) involving BD ( N -H) ranges from 69.8 to 183.6 kJ/mol.