Upon detecting the distinct behavior in molecular recognition processes, particularly in dimer formation in solution, we sought to systematically clarify the structural basis of the process. Intermolecular hydrogen bonding, acknowledged as the primary facilitator of assembly, was quantified in our simulations for individual dimers. To ensure accurate quantification, intramolecular hydrogen bonds, inherently present in each molecular unit, were excluded from our analysis. Typically, a pyrogallolarene unit exhibits 8 intramolecular hydrogen bonds involving OH functionalities, whereas for resorcinarene units, this number is typically around 4. Using this data, we then derived the probability density of the number of intermolecular hydrogen bonds, highlighting the relative stability of hydrogen bonding between two monomers, as depicted in Figure .