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

M. Asakawa, P. R. Ashton, S. Menzer, Francisco Raymo, J. F. Stoddart, A. J P White, D. J. Williams

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Template-directed syntheses of cyclobis(paraquate-4,4'- biphenylene) (1) a molecular square have been achieved by use of π-electron-rich macrocyclic hydroquinone-based and acyclic ferrocene-based 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 topolocally 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
Pages (from-to)877-893
Number of pages17
JournalAngewandte Chemie - International Edition in English
Volume35
Issue number13-14
StatePublished - Jan 1 1996
Externally publishedYes

Fingerprint

Paraquat
Polyethers
Catenanes
Rotaxanes
Electrons
Esters
Derivatives
X ray crystallography
Ultraviolet spectroscopy
Complexation
Self assembly
Nuclear magnetic resonance spectroscopy
Mass spectrometry
Hydrolysis
Hydrogen bonds
Nuclear magnetic resonance
Degradation
Chemical analysis
ferrocene

Keywords

  • catenanes
  • second-sphere coordination
  • self-assembly
  • template syntheses
  • topological stereoisomerism

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Asakawa, M., Ashton, P. R., Menzer, S., Raymo, F., Stoddart, J. F., White, A. J. P., & Williams, D. J. (1996). Cyclobis(paraquat-4,4'-biphenylene) - An organic molecular square. Angewandte Chemie - International Edition in English, 35(13-14), 877-893.

Cyclobis(paraquat-4,4'-biphenylene) - An organic molecular square. / Asakawa, M.; Ashton, P. R.; Menzer, S.; Raymo, Francisco; Stoddart, J. F.; White, A. J P; Williams, D. J.

In: Angewandte Chemie - International Edition in English, Vol. 35, No. 13-14, 01.01.1996, p. 877-893.

Research output: Contribution to journalArticle

Asakawa, M, Ashton, PR, Menzer, S, Raymo, F, Stoddart, JF, White, AJP & Williams, DJ 1996, 'Cyclobis(paraquat-4,4'-biphenylene) - An organic molecular square', Angewandte Chemie - International Edition in English, vol. 35, no. 13-14, pp. 877-893.
Asakawa M, Ashton PR, Menzer S, Raymo F, Stoddart JF, White AJP et al. Cyclobis(paraquat-4,4'-biphenylene) - An organic molecular square. Angewandte Chemie - International Edition in English. 1996 Jan 1;35(13-14):877-893.
Asakawa, M. ; Ashton, P. R. ; Menzer, S. ; Raymo, Francisco ; Stoddart, J. F. ; White, A. J P ; Williams, D. J. / Cyclobis(paraquat-4,4'-biphenylene) - An organic molecular square. In: Angewandte Chemie - International Edition in English. 1996 ; Vol. 35, No. 13-14. pp. 877-893.
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