Structural Diversification of Pillar[n]arene Macrocycles

Despite the fact that pillar[n]arenes receive major interest as building blocks for supramolecular chemistry and advanced materials, their functionalization is generally limited to the modification of the hydroxy or alkoxy units present on the rims. This limited structural freedom restricts further developments and has very recently been overcome. In this article, we highlight three very recent studies demonstrating further structural diversification of pillar[n]arenes by partial removal of the alkoxy substituents on the rims, which can be considered as the next generation of pillar[n]arenes. The next generation: Recent developments made in the field of pillar[n]arene‐based macrocyclic molecules to go beyond single macrocyclic structures with two alkoxy substituents on every benzene ring are highlighted. The recently introduced tiara[n]arenes, leaning pillar[n]arenes, and BowtieArenes with incomplete alkoxy substitution may be regarded as a next step in the structural diversification of pillar[n]arenes.