Catenated Cyclodextrins

Dominique Armspach, Peter R. Ashton, Roberto Ballardini, Vincenzo Balzani, Anna Godi, Christopher P. Moore, Luca Prodi, Neil Spencer, J. Fraser Stoddart, Malcolm S. Tolley, Trevor J. Wear, David J. Williams, J. F. Stoddart

Research output: Contribution to journalArticlepeer-review

81 Scopus citations


A novel synthetic approach is described for the construction of catenanes in aqueous solution from a partially methylated cyclodextrin (CD)‐namely, heptakis(2,6‐di‐O‐methyl‐β‐cyclodextrin) (DM‐β‐CD)‐and a range of substrate molecules that contain a hydrophobic central core in the form of a 4,4′‐disubstituted biphenyl unit (usually bitolyl) carrying two hydrophilic polyether side chains terminated by primary amine functions. In water, the amphiphilic catenane precursors form 1:1 complexes with β‐CD and DM‐β‐CD and 2:1 (guest: host) complexes with the larger γ‐CD. Macrocyclizations of the biphenyl‐containing substrates with aromatic diacid chlorides in aqueous solution and in the presence of DM‐β‐CD under Schotten‐Baumann conditions afforded‐in low yields‐a range of [2]‐ and [3]catenanes. When a consitutionally asymmetrical diamine was employed as the substrate, orientational isomers of a [2]catenane were obtained. A [3]catenene incorporating a macrocyclic tetralactam was found to exist as a mixture of head‐to‐head and head‐to‐tail isomers, which could be separated by high pressure liquid chromatography and identified unambiguously by nuclear magnetic resonance spectroscopy. One of the [2]catenanes afforded good single crystals from which the solid state structure was determined by X‐ray crystallography. Other techniques which aided the characterization of these novel compounds included ultraviolet/visible and luminescence spectroscopy, dynamic nuclear magnetic resonance spectroscopy and fast atom bombardment mass spectrometry. Generally speaking, the catenated cyclodextrins are soluble in halogenated and aromatic hydrocarbons as well as in hydroxylic solvents. The existence of these new compounds gives us a unique insight into the nature of the noncovalent bonding interactions that cyclodextrins employ in binding substrate molecules.

Original languageEnglish (US)
Pages (from-to)33-55
Number of pages23
JournalChemistry – A European Journal
Issue number1
StatePublished - Apr 1995


  • catenanes
  • cyclodextrins
  • macrocycles
  • orientational isomerism

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Organic Chemistry


Dive into the research topics of 'Catenated Cyclodextrins'. Together they form a unique fingerprint.

Cite this