Density functional theory (DFT) computations were performed for dimers of the macrocycle 1 and 2 to understand factors relevant to their self-association. Both 1 (-31.4 kcal mol -1 ) and 2 (-39.6 kcal/mol -1 ) exhibit large negative dimerization energies, suggesting strong interactions between the macrocycles. All computations were performed at B3LYP-D3/6-311+G(d,p)//B3LYP-D3/6-31+G (d) employing Gaussian16. The interaction energy for the dimer of 1 may be attributed to multiple π-interactions between the triple bonds and the arene rings. It is interesting to note that in the optimized geometry for alkyne-arene π-interactions, the alkyne normally resides over the center of the arene ring, but in the fluorinated macrocycle 1 the alkyne moieties reside over the edge of the fluoroarene rings. We hypothesize that this slipped packing helps maximize the number of π-interactions. The stronger interaction energy in the dimer of macrocycle 2 shows that hydrogen bonding plays an important role in stabilizing the packing arrangement. In fact, the computed interaction energy of macrocycle 2 is very close to that reported by Zhong et al. for stacked hexameric macrocycles with multiple hydrogen bonding interactions that drive the dimer formation. Thus, hydrogen bonding can be seen as the decisive factor in the difference in the packing behavior of the macrocycles 2 and 1.