A Redox-Switchable Molecular Zipper

Abstract

The design and synthesis of artificial molecular switches (AMSs) displaying architectures of increased complexity would constitute significant progress in meeting the challenging task of realizing artificial molecular machines (AMMs). Here, we report the synthesis and characterization of a molecular shuttle composed of a cyclobis(paraquat-4,4′-biphenylene) cyclophane ring and a dumbbell incorporating a cyclobis(paraquat-m-phenylene) cyclophane "head" and a bifurcated, tawse-like "tail" composed of two oligoether chains, each containing a 1,5-dioxynaphthalene ring. In its reduced state the ring-in-ring recognition motif, between the meta and para bisradical dicationic cyclophanes (rings), defines the [2]rotaxane, whereas in the oxidized state, the cyclobis(paraquat-4,4′-biphenylene) cyclophane encircles the two 1,5-dioxynaphthalene rings in the bifurcated "tail". The redox-controlled molecular shuttling, which can be likened to the action of a zipper in the macroscopic world, exhibits slow kinetics dampened by the opening and closing of the bifurcated "tail" of the molecular shuttle. Cyclic voltammetry reveals that this slow shuttling is associated with electrochemical hysteresis.