An octacationic homocatenane comprised of two mechanically interlocked cyclobis(paraquat-p-phenylene) rings has been obtained from the oxidation of the septacationic monoradical with nitrosonium hexafluoroantimonate. The nanoconfinement of normally repulsive bipyridinium units results in the enforced π-overlap of eight positively charged pyridinium rings in a volume of <1.25 nm3. In the solid state, the torsional angles around the C-C bonds between the four pairs of pyridinium rings range between 16 and 30°, while the π-π stacking distances between the bipyridinium units are extended for the inside pair and contracted for the pairs on the outside-a consequence of Coulombic repulsion between the inner bipyridinium subunits. In solution, irradiation of the catenane at 275 nm results in electron transfer from one of the paraphenylene rings to the inner bipyridinium dimer, leading to the generation of a temporary mixed-valence state within the rigid and robust homocatenane.
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