Pillar[5]arenes decorated with six-membered-ring aromatics at all the substitution positions

Macrocyclic molecules have characteristic properties different from linear ones, such as high symmetry and guest-inclusion ability. To bring drastic changes to these properties, direct introduction of many substituents is a challenging but effective tool. Herein, we attain direct installation of ten six-membered-ring aromatic π-units into both rims of a pillar[5]arene. In contrast to previous pillar[n]arenes with less hindered five-membered-ring units, which showed conformational complexity and crushed crystal structures, the per-phenyl-substituted pillar[5]arene has a cylinder-shaped crystal structure with a dichloromethane inside the cavity and is obtained as a single pair of D ₅-symmetric enantiomers. The average dihedral angles between the core and peripheral benzene rings sharply increase from 38° to 66°. These differences indicate the importance of local steric repulsion on both rims for determining the structures and properties of macrocycles.