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 pillar[n]arenes, which usually have alkoxy substituents slanting to the cylinder axes. Although alkoxy pillar[5]arenes exist as D5-symmetric enantiomeric pairs, arylated pillar[5]arenes provide crushed single-crystal structures and stereoisomerism including C2-symmetric conformations depending on the aryl groups. Pillar[n]arenes 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 pillar[6]arene instead captures small gaseous molecules in the solid state, probably owing to outside spaces surrounded by aromatic rings.
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