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J Am Chem Soc. 2014 Jul 30;136(30):10569-72. doi: 10.1021/ja505093d. Epub 2014 Jul 21.

Solid-state characterization and photoinduced intramolecular electron transfer in a nanoconfined octacationic homo[2]catenane.

Author information

1
Department of Chemistry and ‡Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208, United States.

Abstract

An octacationic homo[2]catenane 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 nm(3). 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 [2]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 homo[2]catenane.

PMID:
25010450
DOI:
10.1021/ja505093d

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