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

Abstract

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
Pages213-229
Number of pages17
ISBN (Electronic)9783319198279
ISBN (Print)9783319198262
DOIs
StatePublished - Sep 9 2015

Keywords

  • 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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  • Cite this

    Fyfe, M. C. T., Fraser Stoddart, J., & Williams, D. J. (2015). X-ray crystallographic studies on the noncovalent syntheses of supermolecules. In Science of Crystal Structures: Highlights in Crystallography (pp. 213-229). Springer International Publishing. https://doi.org/10.1007/978-3-319-19827-9_23