Finally, the distribution of the different charges was analysed. As we transitioned from neutral monomers to the charged complexes, for the CF 3 case, the C-centered atom becomes more positive due to the electron-withdrawing nature of the substituents. Conversely, in the CH 3 and t Bu cases, the positive charge was delocalised amongst the carbon and nitrogen atoms within the scaffold. Remarkably, in all cases, the hydrogen atom of the NH moiety experiences an increase in positive charge, which facilitates and reinforces the HB interaction. Upon complexation, a charge distribution analysis revealed that for neutral compounds, the only significant change was observed in the carbon atom for CF 3 systems, which becomes less positive. However, for the charged counterparts, a more heterogeneous picture emerges, with the carbon (C) and N1 atoms being the most affected. In the case of CF 3 and CH 3 systems, the central carbon atom generally becomes slightly more positive, while N1 becomes more negative. Conversely, for the t Bu substituent systems, both the carbon (C) and nitrogen (N1) atoms present an increase in negative charge and therefore become less positive. The variations in charge exhibited by the diverse atoms during complexation align remarkably well with the NBO model, as depicted in Figures S1.4 and S1.5. Our findings indicate a discernible but not substantial charge transfer from the examined anions to the N1 and C atoms (LP(X -) -→ BD * (NC)). It is important to note that the magnitude of this charge transfer is consistently lower compared to the corresponding transfer observed in the HB interaction (LP(X -) -→ BD * (NC)).