X-ray crystallographic studies on the noncovalent syntheses of supermolecules

Matthew C T Fyfe, J. Fraser Stoddart*, David J. Williams

*Corresponding author for this work

Research output: Chapter in Book/Report/Conference proceedingChapter


An approach to the supramolecular syntheses of discrete multicomponent aggregates of noncovalently bound molecules, i.e., supermolecules, is described. This approach involved the careful analysis of X-ray crystal structures so as to permit a gradual increase in superstructural complexity. Many elaborate supermolecules were synthesized noncovalently from dialkylammonium-containing cations and crown ethers, following the initial observation that the dibenzylammonium ion threads through dibenzo[24]crown-8 to generate a singly stranded, singly encircled [2]pseudorotaxane, principally as a result of [N+-H...O] and [C-H...O] hydrogen bond formation. The scope of the fundamental recognition motif obtained from this initial observation was then broadened, through the use of thread-like ions with multiple dialkylammonium centers and/or larger crown ethers, so that multiply stranded and/or multiply encircled pseudorotaxanes could be prepared. Cations bearing both dialkylammonium and crown ether recognition sites were also used for the noncovalent synthesis of a discrete daisy chain supermacrocycle and the basic recognition motif was combined with other motifs for the production of a wide range of novel superarchitectures. As a greater understanding of the noncovalent interactions governing the self-assembly of the complex superarchitectures was acquired, new protocols for the noncovalent syntheses of doubly docked pseudorotaxanes and interwoven supramolecular bundles, including a supramolecular analogue of the photosynthetic special pair, were developed. The discovery that anions can play a prominent role in the solid-state self-assembly of some of the supermolecules was a valuable spinoff of the research.

Original languageEnglish (US)
Title of host publicationScience of Crystal Structures
Subtitle of host publicationHighlights in Crystallography
PublisherSpringer International Publishing
Number of pages17
ISBN (Electronic)9783319198279
ISBN (Print)9783319198262
StatePublished - Sep 9 2015


  • Noncovalent interactions
  • Pseudorotaxanes
  • Self-assembly
  • Solid-state structures
  • Supramolecular chemistry

ASJC Scopus subject areas

  • Chemistry(all)
  • Engineering(all)
  • Materials Science(all)
  • Physics and Astronomy(all)


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