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Published February 24, 2016 | Published + Supplemental Material
Journal Article Open

Oligorotaxane Radicals under Orders


A strategy for creating foldameric oligorotaxanes composed of only positively charged components is reported. Threadlike components—namely oligoviologens—in which different numbers of 4,4′-bipyridinium (BIPY^(2+)) subunits are linked by p-xylylene bridges, are shown to be capable of being threaded by cyclobis(paraquat-p-phenylene) (CBPQT^(4+)) rings following the introduction of radical-pairing interactions under reducing conditions. UV/vis/NIR spectroscopic and electrochemical investigations suggest that the reduced oligopseudorotaxanes fold into highly ordered secondary structures as a result of the formation of BIPY•+ radical cation pairs. Furthermore, by installing bulky stoppers at each end of the oligopseudorotaxanes by means of Cu-free alkyne–azide cycloadditions, their analogous oligorotaxanes, which retain the same stoichiometries as their progenitors, can be prepared. Solution-state studies of the oligorotaxanes indicate that their mechanically interlocked structures lead to the enforced interactions between the dumbbell and ring components, allowing them to fold (contract) in their reduced states and unfold (expand) in their fully oxidized states as a result of Coulombic repulsions. This electrochemically controlled reversible folding and unfolding process, during which the oligorotaxanes experience length contractions and expansions, is reminiscent of the mechanisms of actuation associated with muscle fibers.

Additional Information

© 2016 American Chemical Society. This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: November 25, 2015; Published: February 1, 2016. This research is part (Project 34-945) of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdul-Aziz City for Science and Technology (KACST) and Northwestern University (NU). The authors would like to thank both KACST and NU for their continued support of this research. This work was also supported by the National Science Foundation (NSF) under grant no. CHE-1266201. Y.W. thanks the Fulbright Scholar Program for a fellowship and the NU International Institute of Nanotechnology (IIN) for a Ryan Fellowship. The computational studies (W.-G.L., W.A.G.) were supported by NSF (EFRI-ODISSEI 1332411). The authors declare no competing financial interest.

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Supplemental Material - oc5b00377_si_001.pdf


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