The effect of conformational stability on complexation time. To understand why the complexation time of xylene is much shorter than those of dioxane and naphthalene, conformational analyses of the 72 pathways were performed and revealed the involvement of three clusters of the Octacid4 conformations during the Octacid4•xylene self-assembly process at 298 K (Fig. ). The most populated cluster (population: 21/40) had two nearly-orthogonal aromatic linkers that strongly interacted with xylene according to the intermolecular interactions depicted by the noncovalent interaction gradient isosurfaces (Fig. and Movies S1-S2), and the assembly involving this cluster was captured mainly at the early stage of the simulations. The less populated cluster (population: 12/40) had two nearly-parallel, face-to-face aromatic linkers that moderately interacted with xylene (Fig. and Movies S3-S4), and the complexation involving this cluster was captured at the intermediate stage. The least populated cluster (population: 7/40) had two nearly-coplanar aromatic linkers that weakly interacted with xylene (Fig. and Movies S5-S6), and the complexation involving this cluster was captured at the late stage.