Pillar5arenes 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.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.