Sliding-Ring Catenanes

Isurika R. Fernando, Marco Frasconi, Yilei Wu, Wei Guang Liu, Michael R Wasielewski, William A. Goddard, J. Fraser Stoddart

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Template-directed protocols provide a routine approach to the synthesis of mechanically interlocked molecules (MIMs), in which the mechanical bonds are stabilized by a wide variety of weak interactions. In this Article, we describe a strategy for the preparation of neutral [2]catenanes with sliding interlocked electron-rich rings, starting from two degenerate donor-acceptor [2]catenanes, consisting of a tetracationic cyclobis(paraquat-p-phenylene) cyclophane (CBPQT4+) and crown ethers containing either (i) hydroquinone (HQ) or (ii) 1,5-dioxynaphthalene (DNP) recognition units and carrying out four-electron reductions of the cyclophane components to their neutral forms. The donor-acceptor interactions between the CBPQT4+ ring and both HQ and DNP units present in the crown ethers that stabilize the [2]catenanes are weakened upon reduction of the cyclophane components to their radical cationic states and are all but absent in their fully reduced states. Characterization in solution performed by UV-vis, EPR, and NMR spectroscopic probes reveals that changes in the redox properties of the [2]catenanes result in a substantial decrease of the energy barriers for the circumrotation and pirouetting motions of the interlocked rings, which glide freely through one another in the neutral states. The solid-state structures of the fully reduced catenanes reveal profound changes in the relative dispositions of the interlocked rings, with the glycol chains of the crown ethers residing in the cavities of the neutral CBPQT0 rings. Quantum mechanical investigations of the energy levels associated with the four different oxidation states of the catenanes support this interpretation. Catenanes and rotaxanes with sliding rings are expected to display unique properties.

Original languageEnglish
Pages (from-to)10214-10225
Number of pages12
JournalJournal of the American Chemical Society
Volume138
Issue number32
DOIs
Publication statusPublished - Aug 17 2016

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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    Fernando, I. R., Frasconi, M., Wu, Y., Liu, W. G., Wasielewski, M. R., Goddard, W. A., & Stoddart, J. F. (2016). Sliding-Ring Catenanes. Journal of the American Chemical Society, 138(32), 10214-10225. https://doi.org/10.1021/jacs.6b04982