Chemically and Electrochemically Triggered Assembly of Viologen Radicals: Towards Multiaddressable Molecular Switches

We have established that bipyridinium radicals can be reversibly pi-dimerized under the combined effects of chemical (proton transfer) and electrochemical (electron transfer) stimuli. Our investigations also led to the discovery that a bis-pyridinyl appended calixarene intermediate is involved in a fully reversible redox-triggered sigma-dimerization process. The structure of the most stable intramolecular sigma-dimer was provided by computational chemistry and its complete conversion into a noncovalent pi-dimer could be triggered chemically by addition of protons, leading to the formation of protonated cation radicals. Theoretical data collected with the N-methylated and N-protonated pi-dimers also support the existence of multivariant orientations in pi-bonded dimers of viologen cation-radicals.