Cation controlled rotation in anionic pillar[5]arenes and its application for fluorescence switch

Controlling molecular motion is one of hot topics in the field of chemistry. Molecular rotors have wide applications in building nanomachines and functional materials, due to their controllable rotations. Hence, the development of novel rotor systems, controlled by external stimuli, is desirable. Pillar[n]arenes, a class of macrocycles, have a unique planar chirality, in which two stable conformational isomers pR and pS would interconvert by oxygen-through-the-annulus rotations of their hydroquinone rings. We observe the differential kinetic traits of planar chirality transformation in sodium carboxylate pillar[5]arene (WP5-Na) and ammonium carboxylate pillar[5]arene (WP5-NH(4)), which inspire us to construct a promising rotary platform in anionic pillar[5]arenes (WP5) skeletons. Herein, we demonstrate the non-negligible effect of counter cations on rotational barriers of hydroquinone rings in WP5, which enables a cation grease/brake rotor system. Applications of this tunable rotor system as fluorescence switch and anti-counterfeiting ink are further explored.