Radically enhanced molecular switches

The mechanism governing the redox-stimulated switching behavior of a tristable [2]rotaxane consisting of a cyclobis(paraquat-p-phenylene) (CBPQT ⁴⁺) ring encircling a dumbbell, containing tetrathiafulvalene (TTF) and 1,5-dioxynaphthalene (DNP) recognition units which are separated from each other along a polyether chain carrying 2,6-diisopropylphenyl stoppers by a 4,4′-bipyridinium (BIPY ²⁺) unit, is described. The BIPY ²⁺ unit acts to increase the lifetime of the metastable state coconformation (MSCC) significantly by restricting the shuttling motion of the CBPQT ⁴⁺ ring to such an extent that the MSCC can be isolated in the solid state and is stable for weeks on end. As controls, the redox-induced mechanism of switching of two bistable [2]rotaxanes and one bistable [2]catenane composed of CBPQT ⁴⁺ rings encircling dumbbells or macrocyclic polyethers, respectively, that contain a BIPY ²⁺ unit with either a TTF or DNP unit, is investigated. Variable scan-rate cyclic voltammetry and digital simulations of the tristable and bistable [2]rotaxanes and [2]catenane reveal a mechanism which involves a bisradical state coconformation (BRCC) in which only one of the BIPY ^•+ units in the CBPQT ^2(•+) ring is oxidized to the BIPY ²⁺ dication. This observation of the BRCC was further confirmed by theoretical calculations as well as by X-ray crystallography of the [2]catenane in its bisradical tetracationic redox state. It is evident that the incorporation of a kinetic barrier between the donor recognition units in the tristable [2]rotaxane can prolong the lifetime and stability of the MSCC, an observation which augurs well for the development of nonvolatile molecular flash memory devices.