Supramolecular daisy chains

S. J. Cantrill, G. J. Youn, J. F. Stoddart*, D. J. Williams

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

130 Scopus citations

Abstract

Two series of self-complementary daisy chain monomers, in which a secondary ammonium ion-containing arm is grafted onto a macrocycle with either a [24]- or [25]crown-8 constitution, have been synthesized. In the solid- and 'gas'-phases, the parent [24]crown-8-based monomer forms dimeric superstructures, as revealed by X-ray crystallography and mass spectrometry, respectively. Elucidation of the complicated solution-phase behavior of this compound was facilitated by the synthesis and study of both deuterated, and fluorinated, analogues. These investigations revealed that the cyclic dimeric superstructure also dominates in solution, except when extremes of either concentration (low), temperature (high), or solvent polarity (highly polar, e.g., dimethyl sulfoxide) are employed. Whereas, upon aggregation, the [24]crown-8-based daisy chain monomers have the capacity to form stereoisomeric superstructures further complicating the study of this series of compounds. The assembly of [25]crown-8-based monomers gives only achiral superstructures. The weaker association exhibited between secondary dialkylammonium ions and crown ethers with a [25]crown-8 constitution, however, resulted in limited oligomerization-only dimeric and trimeric superstructures were formed at experimentally attainable concentrations-of [25]crown-8-based daisy chain monomers.

Original languageEnglish (US)
Pages (from-to)6857-6872
Number of pages16
JournalJournal of Organic Chemistry
Volume66
Issue number21
DOIs
StatePublished - Oct 19 2001

ASJC Scopus subject areas

  • Organic Chemistry

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