Anion- and Solvent-Induced Rotary Dynamics and Sensing in a Perylene Diimide [3]Catenane.

ABSTRACT

A novel dynamic [3]catenane consisting of a large four-station central macrocycle which incorporates a bay tetrachloro-functionalized perylene diimide (PDI) unit and two triazolium anion-binding motifs, mechanically bonded with two smaller isophthalamide-containing macrocycles, is constructed using an anion template synthetic methodology. Proton NMR, electronic absorption, and fluorescence emission spectroscopies together with molecular dynamics simulations are used to investigate the anion recognition- and solvent-dependent dynamic properties of the higher-order mechanically interlocked molecule. Importantly, unprecedented solvent-dependent and anion-binding-induced circumrotatory motion in a hetero[3]catenane system is demonstrated where the exotic dual rotary switching behavior provides a unique and sophisticated mechanism for optical anion sensing in competitive protic organic and aqueous-organic media.