Per-Arylation of Pillarnarenes: An Effective Tool to Modify the Properties of Macrocycles

Installation of various substituents is a reliable and versatile way to alter the properties of macrocyclic molecules, but high-yield and controlled methods are not always available especially for multifold reactions. Herein, we report 10- and 12-fold introduction of aryl substituents onto both rims of cylinder-shaped pillarnarenes, which usually have alkoxy substituents slanting to the cylinder axes. Although alkoxy pillar5arenes exist as D5-symmetric enantiomeric pairs, arylated pillar5arenes provide crushed single-crystal structures and stereoisomerism including C2-symmetric conformations depending on the aryl groups. Pillarnarenes with 2-benzofuranyl groups display bright fluorescence with quantum yields of 88-90% and no host-guest complexation with electron-deficient molecules in solution due to large deviation from alkoxy compounds. A benzofuran-appended pillar6arene instead captures small gaseous molecules in the solid state, probably owing to outside spaces surrounded by aromatic rings.