Cyclobis(paraquat-4,4′-biphenylene) - An organic molecular square

Masumi Asakawa, Peter R. Ashton, Stephan Menzer, Françisco M. Raymo, J. Fraser Stoddart, Andrew J.P. White, David J. Williams

Research output: Contribution to journalArticle

77 Scopus citations

Abstract

Template-directed syntheses of cyclobis(paraquat-4,4′-biphenylene) (1) - a molecular square - have been achieved by use of π-electron-rich macrocyclic hydroquinone-based and acyclic ferrocenebased templates. In particular, the use of a polyether-disubstituted ferrocene derivative as a template permits synthesis of 1 (which is accessible only in very low yields without templates) on a preparative scale. Furthermore, the use of a macrocyclic hydroquinone-based polyether template incorporating an ester function in one polyether chain - an "oriented" macrocycle - affords a 1:1 mixture of two topologically stereoisomeric [3]catenanes. Ester hydrolysis of the π-electron-rich macrocyclic components mechanically interlocked with 1 within the catenated structures releases the tetracationic cyclophane in quantitative yield as a result of the degradation of the [3]catenanes. The molecular square has been characterized by X-ray crystallography, FAB mass spectrometry, 1H NMR and 13C NMR spectroscopies, and elemental analysis. The binding properties of 1 and of the smaller cyclophane cyclobis(paraquat-p- phenylene) toward a series of π-electron-rich guests have also been investigated with the above techniques and UV/VIS spectroscopy. The self-assembly of the resulting supramolecular complexes in solution and in the solid state is driven mainly by π-π stacking interactions and hydrogen-bonding interactions, as well as by edge-to-face T-type interactions. In particular, the complexation of ferrocene or a ferrocene-based derivative within the cavity of 1 suggests the possibility of constructing functioning ferrocene-based molecular and supramolecular devices that can be controlled electrochemically in the form of catenanes, rotaxanes, and pseudorotaxanes.

Original languageEnglish (US)
Pages (from-to)877-893
Number of pages17
JournalChemistry - A European Journal
Volume2
Issue number7
DOIs
StatePublished - Dec 1 1996
Externally publishedYes

Keywords

  • Catenanes
  • Second-sphere coordination
  • Self-assembly
  • Template syntheses
  • Topological stereoisomerism

ASJC Scopus subject areas

  • Chemistry(all)

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    Asakawa, M., Ashton, P. R., Menzer, S., Raymo, F. M., Stoddart, J. F., White, A. J. P., & Williams, D. J. (1996). Cyclobis(paraquat-4,4′-biphenylene) - An organic molecular square. Chemistry - A European Journal, 2(7), 877-893. https://doi.org/10.1002/chem.19960020720