Catenation through a Combination of Radical Templation and Ring-Closing Metathesis

Ian C. Gibbs-Hall, Nicolaas A. Vermeulen, Edward J. Dale, James J. Henkelis, Anthea K. Blackburn, Jonathan C. Barnes, J. Fraser Stoddart*

*Corresponding author for this work

Research output: Contribution to journalArticle

19 Scopus citations

Abstract

Synthesis of an electrochemically addressable [2]catenane has been achieved following formation by templation of a [2]pseudorotaxane employing radically enhanced molecular recognition between the bisradical dication obtained on reduction of the tetracationic cyclophane, cyclobis(paraquat-p-phenylene), and the radical cation generated on reduction of a viologen disubstituted with p-xylylene units, both carrying tetraethylene glycol chains terminated by allyl groups. This inclusion complex was subjected to olefin ring-closing metathesis, which was observed to proceed under reduced conditions, to mechanically interlock the two components. Upon oxidation, Coulombic repulsion between the positively charged and mechanically interlocked components results in the adoption of a co-conformation where the newly formed alkene resides inside the cavity of the tetracationic cyclophane. 1H NMR spectroscopic analysis of this hexacationic [2]catenane shows a dramatic upfield shift of the resonances associated with the olefinic and allylic protons as a result of them residing inside the tetracationic component. Further analysis shows high diastereoselectivity during catenation, as only a single (Z)-isomer is formed.

Original languageEnglish (US)
Pages (from-to)15640-15643
Number of pages4
JournalJournal of the American Chemical Society
Volume137
Issue number50
DOIs
StatePublished - Dec 23 2015

ASJC Scopus subject areas

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

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    Gibbs-Hall, I. C., Vermeulen, N. A., Dale, E. J., Henkelis, J. J., Blackburn, A. K., Barnes, J. C., & Stoddart, J. F. (2015). Catenation through a Combination of Radical Templation and Ring-Closing Metathesis. Journal of the American Chemical Society, 137(50), 15640-15643. https://doi.org/10.1021/jacs.5b10623