Unsupervised machine learning of the ionic environments that emerge within the superlattice allowed to detect three distinct ionic domains differeing in terms of structural order, persistence, and dynamics (Figure ). In particular, the CIT ions at the NP-NP interface work as bonding EAs, stabilizing the FCC lattice. On the other hand, the CIT ions in the octahedral and tetrahedral cavities of the FCC lattice are more dynamic and prone to behave as EAs (Figures and). Reconstruction of the microscopic dynamics of CIT ions in the system correlates the transition to the conductive regime to the emergence of ionic gates connecting the tetrahedral and octahedral cavities in the FCC superlattice through which the CIT charge carriers can diffuse. The transition matrices of Figures demonstrate a supramolecular behavior reminiscent of the mechanism of conduction of metals. In particular, in conductive regime, the "blue" CIT ions at the NP-NP interface interconnect the NPs and keep the lattice stable, while the CIT ions in the cavities behave as the conductive EAs.