The influence of macrocyclic polyether constitution upon ammonium ion/crown ether recognition processes

Stuart J. Cantrill, David A. Fulton, Aaron M. Heiss, Anthony R. Pease, J. Fraser Stoddart*, Andrew J P White, David J. Williams

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

91 Scopus citations


Secondary dialkylammonium (R2NH2+) ions are hound readily by dibenzo[24]crown-8 (DB24C8) to form threaded complexes, namely [2]pseudorotaxanes. The effect of replacing one or both of the catechol rings in DB24C8 with resorcinol rings upon the crown ether's ability to bind R2NH2+ ions has now been investigated. When only one aromatic ring is changed from catechol to resorcinol, a crown ether with a [25]crown-8 constitution is created - namely benzometaphenylene[25]crown-8 (BMP25C8). A [2]pseudorotaxane is formed in the solid state when BMP25C8 is co-crystallized with dibenzylammonium hexafluorophosphate, as evidenced by its X-ray crystal structure. Furthermore, this crown ether has been shown to bind R2NH2+ ions in solution, an observation which has been exploited in the synthesis of the first BMP25C8-containing [2]rotaxane. The methodology employed to generate this [2]rotaxane - the reaction of an amine with an isocyanate to form a urea - was tested initially on a system incorporating DB24C8 and was shown to work efficiently. Both [2]rolaxanes have been fully characterized by 1H and 13C NMR spectroscopies, FAB mass spectrometry and X-ray crystallography. Interestingly, the unsymmetrical nature of the dumbbell-shaped component in each of the two [2]rotaxanes renders each face of the encircling macrocyclic polyether diastereotopic, a feature that is apparent upon inspection of their 1H NMR spectra. The resonances associated with the diastereotopic protons on each face of the macrorings are well enough resolved to enable the faces of the crown ethers to be readily identified with respect to their protons by 1H NMR spectroscopy. Unambiguous assignments can be made as a result of the fact that the protons on each face of the macrocyclic polyether experience a unique set of through-space interactions, as evidenced by T-ROESY experiments. Additionally, the two-dimensional NMR analyses are in agreement with the X-ray crystallographic studies performed on these [2]rotaxanes, indicating that the crown ethers are located intimately around the NH2+ centers as expected. Replacement of both catechol rings in the DB24C8 constitution with resorcinol rings results in a crown ether with a [26]crown-8 constitution - namely bismetaphenylene[26]crown-8 (BMP26C8). All the evidence to date points to the fact that this further change in constitution results in a crown ether that does not bind R2NH2+ ions in either the solution or solid states.

Original languageEnglish (US)
Pages (from-to)2274-2287
Number of pages14
JournalChemistry - A European Journal
Issue number12
StatePublished - Jun 16 2000


  • Crown ethers
  • Hydrogen bonds
  • Rotaxanes
  • Secondary ammonium ions
  • Self-assembly

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry


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