A redox-switchable α-cyclodextrin-based [2]rotaxane

Yan Li Zhao, William R. Dichtel, Ali Trabolsi, Sourav Saha, Ivan Aprahamian, J. Fraser Stoddart

Research output: Contribution to journalArticle

Abstract

A bistable [2]rotaxane comprising an α-cyclodextrin (α-CD) ring and a dumbbell component containing a redox-active tetrathiafulvalene (TTF) ring system within its rod section has been synthesized using the Cu(I)-catalyzed azide-alkyne cycloaddition, and the redox-driven movements of the α-CD ring between the TTF and newly formed triazole ring systems have been elucidated. Microcalorimetric titrations on model complexes suggested that the α-CD ring prefers to reside on the TTF rather than on the triazole ring system by at least an order of magnitude. The fact that this situation does pertain in the bistable [2]rotaxane has not only been established quantitatively by electrochemical experiments and backed up by spectroscopic and chiroptical measurements but also been confirmed semiquantitatively by the recording of numerous cyclic voltammograms which point, along with the use of redox-active chemical reagents, to a mechanism of switching that involves the oxidation of the neutral TTF ring system to either its radical cationic (TTF•+) or dicationic (TTF2+) counterparts, whereupon the α-CD ring, moves along the dumbbell to encircle the triazole ring system. Since redox control by both chemical and electrochemical means is reversible, the switching by the bistable [2]rotaxane can be reversed on reduction of the TTF•+ or TTF2+ back to being a neutral TTF.

Original languageEnglish (US)
Pages (from-to)11294-11296
Number of pages3
JournalJournal of the American Chemical Society
Volume130
Issue number34
DOIs
StatePublished - Aug 27 2008

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Rotaxanes
Cyclodextrins
Oxidation-Reduction
Triazoles
Cycloaddition
Titration
Alkynes
Azides
Cycloaddition Reaction
Oxidation
tetrathiafulvalene
Experiments

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Zhao, Y. L., Dichtel, W. R., Trabolsi, A., Saha, S., Aprahamian, I., & Stoddart, J. F. (2008). A redox-switchable α-cyclodextrin-based [2]rotaxane. Journal of the American Chemical Society, 130(34), 11294-11296. https://doi.org/10.1021/ja8036146

A redox-switchable α-cyclodextrin-based [2]rotaxane. / Zhao, Yan Li; Dichtel, William R.; Trabolsi, Ali; Saha, Sourav; Aprahamian, Ivan; Stoddart, J. Fraser.

In: Journal of the American Chemical Society, Vol. 130, No. 34, 27.08.2008, p. 11294-11296.

Research output: Contribution to journalArticle

Zhao, YL, Dichtel, WR, Trabolsi, A, Saha, S, Aprahamian, I & Stoddart, JF 2008, 'A redox-switchable α-cyclodextrin-based [2]rotaxane', Journal of the American Chemical Society, vol. 130, no. 34, pp. 11294-11296. https://doi.org/10.1021/ja8036146
Zhao YL, Dichtel WR, Trabolsi A, Saha S, Aprahamian I, Stoddart JF. A redox-switchable α-cyclodextrin-based [2]rotaxane. Journal of the American Chemical Society. 2008 Aug 27;130(34):11294-11296. https://doi.org/10.1021/ja8036146
Zhao, Yan Li ; Dichtel, William R. ; Trabolsi, Ali ; Saha, Sourav ; Aprahamian, Ivan ; Stoddart, J. Fraser. / A redox-switchable α-cyclodextrin-based [2]rotaxane. In: Journal of the American Chemical Society. 2008 ; Vol. 130, No. 34. pp. 11294-11296.
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