In the case of pyrogallolarene, the data suggests that forming dimeric species (states B P , C P , and D P ) is less thermodynamically favored compared to scenarios where monomers are in isolated diffusion (state A P ). Contrarily, for resorcinarene, the emergence of two distinct free energy minima associated with the formation of 2 dimers (DI = 2 -state A R ) or 3 dimers (DI = 3 -state B R ), with a relative free energy change of ∆F 3←2 = -6, kcal/mol, indicates a Figure : Free energy surfaces for resorcinarene (right) and pyrogallolarene (left) assembly process. From the representation of the two FESs it appears evident the sensible difference in the two calixarenes assembly processes, where some states does not have a geometric equivalent in both systems.