Molecular meccano, 49. - Pseudorotaxanes and catenanes containing a redox-active unit derived from tetrathiafulvalene

Masumi Asakawa, Peter R. Ashton, Vincenzo Balzani, Sue E. Boyd, Alberto Credi, Gunter Mattersteig, Stephan Menzer, Marco Montalti, Francisco Raymo, Cristina Ruffilli, J. Fraser Stoddart, Margherita Venturi, David J. Williams

Research output: Contribution to journalArticle

66 Citations (Scopus)

Abstract

Two bis(2-oxy-1,3-propylenedithio)tetrathiafulvalene-containing acyclic polyethers and two macrocyclic polyethers, each incorporating one bis(2-oxy- 1,3-propylenedithio)tetrathiafulvalene unit and one p-phenylene ring, have been synthesized. The two acyclic polyethers are bound by cyclobis(paraquat- p-phenylene) with pseudorotaxane geometries in solution. The two macrocyclic polyethers have been mechanically interlocked with this tetracationic cyclophane to form [2]catenanes in a kinetically controlled self-assembly process. The X-ray crystallographic analysis of one of the two [2]catenanes and 1H-NMR-spectroscopic studies of both compounds showed that the p- phenylene ring of the macrocyclic polyether is located inside the cavity of the tetracationic cyclophane, while the bis(2-oxy-1,3- propylenedithio)tetrathiafulvalene unit resides alongside. The [2]pseudorotaxanes and [2]catenanes show broad bands around 780 nm, arising from the charge-transfer (CT) interaction between the electron-donor tetrathiafulvalene-(TTF-)type unit and the electron-acceptor units of the tetracationic cyclophane. 1H-NMR-spectroscopic studies have shown that the [2]pseudorotaxanes dissociate into their separate components upon oxidation of the TTF-type unit, as a result of disruption of the CT interaction and electrostatic repulsion between the tetracationic host and the newly formed monocationic guest. The subsequent reduction of the guest to its neutral state affords back the pseudorotaxane-type complex restoring the original equilibrium. The results obtained from electrochemical experiments are consistent with the reversible, redox-driven dethreading/rethreading process observed by 1H-NMR spectroscopy. Variable-temperature 1H-NMR-spectroscopic investigations have revealed two dynamic processes, both involving the relative movements of the mechanically interlocked components in the [2]catenanes. The two consecutive oxidation processes involving the TTF-type unit, observed electrochemically, are displaced toward more positive potentials compared with the free cyclic polyethers. The two reversible two- electron reduction processes, characteristic of free cyclobis(paraquat-p- phenylene), separate into four reversible one-electron processes because of the topological difference between the 'inside' and 'alongside' electron- acceptor units in the [2]catenane.

Original languageEnglish
Pages (from-to)985-994
Number of pages10
JournalEuropean Journal of Organic Chemistry
Issue number5
StatePublished - Jan 1 1999
Externally publishedYes

Fingerprint

Catenanes
Rotaxanes
Polyethers
nuclear magnetic resonance
Electrons
Paraquat
electrons
Nuclear magnetic resonance
charge transfer
Charge transfer
oxidation
rings
Oxidation
self assembly
Self assembly
Nuclear magnetic resonance spectroscopy
Oxidation-Reduction
tetrathiafulvalene
interactions
Electrostatics

Keywords

  • Catenanes
  • Molecular machines
  • Pseudorotaxanes
  • Template-directed synthesis
  • Tetrathiafulvalenes

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Asakawa, M., Ashton, P. R., Balzani, V., Boyd, S. E., Credi, A., Mattersteig, G., ... Williams, D. J. (1999). Molecular meccano, 49. - Pseudorotaxanes and catenanes containing a redox-active unit derived from tetrathiafulvalene. European Journal of Organic Chemistry, (5), 985-994.

Molecular meccano, 49. - Pseudorotaxanes and catenanes containing a redox-active unit derived from tetrathiafulvalene. / Asakawa, Masumi; Ashton, Peter R.; Balzani, Vincenzo; Boyd, Sue E.; Credi, Alberto; Mattersteig, Gunter; Menzer, Stephan; Montalti, Marco; Raymo, Francisco; Ruffilli, Cristina; Stoddart, J. Fraser; Venturi, Margherita; Williams, David J.

In: European Journal of Organic Chemistry, No. 5, 01.01.1999, p. 985-994.

Research output: Contribution to journalArticle

Asakawa, M, Ashton, PR, Balzani, V, Boyd, SE, Credi, A, Mattersteig, G, Menzer, S, Montalti, M, Raymo, F, Ruffilli, C, Stoddart, JF, Venturi, M & Williams, DJ 1999, 'Molecular meccano, 49. - Pseudorotaxanes and catenanes containing a redox-active unit derived from tetrathiafulvalene', European Journal of Organic Chemistry, no. 5, pp. 985-994.
Asakawa, Masumi ; Ashton, Peter R. ; Balzani, Vincenzo ; Boyd, Sue E. ; Credi, Alberto ; Mattersteig, Gunter ; Menzer, Stephan ; Montalti, Marco ; Raymo, Francisco ; Ruffilli, Cristina ; Stoddart, J. Fraser ; Venturi, Margherita ; Williams, David J. / Molecular meccano, 49. - Pseudorotaxanes and catenanes containing a redox-active unit derived from tetrathiafulvalene. In: European Journal of Organic Chemistry. 1999 ; No. 5. pp. 985-994.
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AU - Boyd, Sue E.

AU - Credi, Alberto

AU - Mattersteig, Gunter

AU - Menzer, Stephan

AU - Montalti, Marco

AU - Raymo, Francisco

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AU - Stoddart, J. Fraser

AU - Venturi, Margherita

AU - Williams, David J.

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