To conclude, in our comprehensive investigation into the assembly processes of resorcinarene and pyrogallolarene, we have identified marked thermodynamic differences that differentiate the two systems. Our findings underscore the pivotal role of dimer formation in dictating the self-assembly mechanism. A key revelation was the delicate balance Figure : Analysis of the encapsulated solvent molecules in calixarene capsules. We can see that resorcinarene has a strong tendency in incorporating 8 chloroform molecules, while pyrogallolarene usually includes 1-2 molecules more. between intermolecular and intramolecular hydrogen bonding in determining this dimeric species formation. Water, while being an essential component in facilitating the assembly of resorcinarene, appears to influence the kinetics minimally due to its rapid diffusive behavior, differentiating it from the more deliberate assembly mechanisms of the calixarenes. Exploring solvent encapsulation, we discerned that pyrogallolarene capsules can accommodate approximately one to two additional chloroform molecules compared to their resorcinarene counterparts. This increased accommodation capacity can be attributed to the lesser steric constraints imposed by the absence of water molecules within the pyrogallolarene structure. Notably, our computational results indicate a discrepancy with experimental data, suggesting that traditionally reported values may underestimate the number of encapsulated solvent molecules by around two units. This study, while detailed, is pivotal as it bridges gaps in our understanding and provides detailed insights into the intricacies of the assembly process of these systems. Our findings offer both a deepening and refinement of experimental characterizations, presenting a complementary viewpoint with atomistic detail. The versatility 13 and rigor of the methodology we have established suggest its potential use across a diverse range of assembly processes. This encompasses other calixarene-based systems and extends to wider fields in chemistry and catalysis, paving the way to address the intricate questions of compartmentalization in biological settings.