With these newly defined CVs, we aim to elucidate the process, effectively distinguishing between individual dimer formations and extensive assembly states. This approach delivers a comprehensive insight into the associated free energy landscape. The two FESs presented in the study reveal distinct characteristics, suggesting different self-assembly pathways between pyrogallolarene and resorcinarene. Our investigation focuses Figure : CVs used in enhanced sampling and analysis. On top we can find the biasing CVs, on which the bias potential of metadynamics have been built. In the bottom of the figure, we show a graphical representation of the CVs used in analysis, tailored to detect the assembly process of calixarene capsules, combining orientation and distance of monomers. on the initial stages of self-assembly, specifically when the Growth Index is approximately 0.