Recognition of Bipyridinium-Based Derivatives by Hydroquinone-and/or Dioxynaphthalene-Based Macrocyclic Polyethers: From Inclusion Complexes to the Self-Assembly of [2]Catenanes

Masumi Asakawa, Peter R. Ashton, Sue E. Boyd, Christopher L. Brown, Richard E. Gillard, Oldrich Kocian, Francisco Raymo, J. Fraser Stoddart, Malcolm S. Tolley, Andrew J P White, David J. Williams

Research output: Contribution to journalArticle

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Abstract

A range of π-electron-rich macrocyclic polyethers incorporating dioxybenzene (hydroquinone) and/or dioxynaphthalene units have been synthesized in good yields by simple two-step procedures. These macrocycles are able to bind bipyridinium-based guests as a result of a series of cooperative noncovalent bonding interactions. These molecular recognition events can be extended to the self-assembly of [2]catenanes incorporating the bipyridinium-based cyclophane, cyclobis(paraquat-p-phenylene), and the macrocyclic polyethers incorporating dioxybenzene and -naphthalene units. The efficiencies of these self-assembly processes were found to depend upon the stereoelectronic features of the π-electron-rich macrocycles-namely, the nature and the substitution pattern of the aromatic units. X-ray crystallographic analysis of some of these [2]catenanes proved unequivocally the relative geometries of the interlocked components. In addition, in the case of those asymmetric [2]catenanes incorporating two different aromatic units within their macrocyclic polyether components, only one of the expected two translational isomers was observed in the solid state. In particular, in all the structures examined, the 1,4-dioxybenzene and 1,5-dioxynaphthalene units are located within the cavity of the tetracationic cyclophane component in preference to other regioisomeric dioxynaphthalene units that reside alongside. Variable-temperature 1H NMR spectroscopic investigation of the geometries adopted by these [2]catenanes in solution revealed the same selectivity that was observed for one translational isomer over another in the solid state.

Original languageEnglish
Pages (from-to)26-37
Number of pages12
JournalJournal of Organic Chemistry
Volume62
Issue number1
StatePublished - Dec 1 1997
Externally publishedYes

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Catenanes
Polyethers
Self assembly
Derivatives
Isomers
Molecular recognition
Paraquat
Geometry
Electrons
Substitution reactions
Nuclear magnetic resonance
X rays
hydroquinone

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Recognition of Bipyridinium-Based Derivatives by Hydroquinone-and/or Dioxynaphthalene-Based Macrocyclic Polyethers : From Inclusion Complexes to the Self-Assembly of [2]Catenanes. / Asakawa, Masumi; Ashton, Peter R.; Boyd, Sue E.; Brown, Christopher L.; Gillard, Richard E.; Kocian, Oldrich; Raymo, Francisco; Stoddart, J. Fraser; Tolley, Malcolm S.; White, Andrew J P; Williams, David J.

In: Journal of Organic Chemistry, Vol. 62, No. 1, 01.12.1997, p. 26-37.

Research output: Contribution to journalArticle

Asakawa, M, Ashton, PR, Boyd, SE, Brown, CL, Gillard, RE, Kocian, O, Raymo, F, Stoddart, JF, Tolley, MS, White, AJP & Williams, DJ 1997, 'Recognition of Bipyridinium-Based Derivatives by Hydroquinone-and/or Dioxynaphthalene-Based Macrocyclic Polyethers: From Inclusion Complexes to the Self-Assembly of [2]Catenanes', Journal of Organic Chemistry, vol. 62, no. 1, pp. 26-37.
Asakawa, Masumi ; Ashton, Peter R. ; Boyd, Sue E. ; Brown, Christopher L. ; Gillard, Richard E. ; Kocian, Oldrich ; Raymo, Francisco ; Stoddart, J. Fraser ; Tolley, Malcolm S. ; White, Andrew J P ; Williams, David J. / Recognition of Bipyridinium-Based Derivatives by Hydroquinone-and/or Dioxynaphthalene-Based Macrocyclic Polyethers : From Inclusion Complexes to the Self-Assembly of [2]Catenanes. In: Journal of Organic Chemistry. 1997 ; Vol. 62, No. 1. pp. 26-37.
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abstract = "A range of π-electron-rich macrocyclic polyethers incorporating dioxybenzene (hydroquinone) and/or dioxynaphthalene units have been synthesized in good yields by simple two-step procedures. These macrocycles are able to bind bipyridinium-based guests as a result of a series of cooperative noncovalent bonding interactions. These molecular recognition events can be extended to the self-assembly of [2]catenanes incorporating the bipyridinium-based cyclophane, cyclobis(paraquat-p-phenylene), and the macrocyclic polyethers incorporating dioxybenzene and -naphthalene units. The efficiencies of these self-assembly processes were found to depend upon the stereoelectronic features of the π-electron-rich macrocycles-namely, the nature and the substitution pattern of the aromatic units. X-ray crystallographic analysis of some of these [2]catenanes proved unequivocally the relative geometries of the interlocked components. In addition, in the case of those asymmetric [2]catenanes incorporating two different aromatic units within their macrocyclic polyether components, only one of the expected two translational isomers was observed in the solid state. In particular, in all the structures examined, the 1,4-dioxybenzene and 1,5-dioxynaphthalene units are located within the cavity of the tetracationic cyclophane component in preference to other regioisomeric dioxynaphthalene units that reside alongside. Variable-temperature 1H NMR spectroscopic investigation of the geometries adopted by these [2]catenanes in solution revealed the same selectivity that was observed for one translational isomer over another in the solid state.",
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AU - Asakawa, Masumi

AU - Ashton, Peter R.

AU - Boyd, Sue E.

AU - Brown, Christopher L.

AU - Gillard, Richard E.

AU - Kocian, Oldrich

AU - Raymo, Francisco

AU - Stoddart, J. Fraser

AU - Tolley, Malcolm S.

AU - White, Andrew J P

AU - Williams, David J.

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