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

A bistable [2]rotaxane comprising an alpha-cyclodextrin (alpha-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 alph...

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Main Authors: Dichtel, William R., Zhao, Yanli, Trabolsi, Ali, Saha, Sourav, Aprahamian, Ivan, Stoddart, J. Fraser
Other Authors: School of Physical and Mathematical Sciences
Format: Article
Language:English
Published: 2011
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Online Access:https://hdl.handle.net/10356/92174
http://hdl.handle.net/10220/7042
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Institution: Nanyang Technological University
Language: English
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spelling sg-ntu-dr.10356-921742020-03-07T12:31:29Z A redox-switchable α-cyclodextrin-based [2]rotaxane Dichtel, William R. Zhao, Yanli Trabolsi, Ali Saha, Sourav Aprahamian, Ivan Stoddart, J. Fraser School of Physical and Mathematical Sciences DRNTU::Science::Biological sciences::Biochemistry A bistable [2]rotaxane comprising an alpha-cyclodextrin (alpha-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 alpha-CD ring between the TTF and newly formed triazole ring systems have been elucidated. Microcalorimetric titrations on model complexes suggested that the alpha-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 alpha-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. 2011-09-13T03:57:17Z 2019-12-06T18:18:39Z 2011-09-13T03:57:17Z 2019-12-06T18:18:39Z 2008 2008 Journal Article 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. 0002-7863 https://hdl.handle.net/10356/92174 http://hdl.handle.net/10220/7042 10.1021/ja8036146 159739 en Journal of the American chemical society © 2008 American Chemical Society 3 p.
institution Nanyang Technological University
building NTU Library
country Singapore
collection DR-NTU
language English
topic DRNTU::Science::Biological sciences::Biochemistry
spellingShingle DRNTU::Science::Biological sciences::Biochemistry
Dichtel, William R.
Zhao, Yanli
Trabolsi, Ali
Saha, Sourav
Aprahamian, Ivan
Stoddart, J. Fraser
A redox-switchable α-cyclodextrin-based [2]rotaxane
description A bistable [2]rotaxane comprising an alpha-cyclodextrin (alpha-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 alpha-CD ring between the TTF and newly formed triazole ring systems have been elucidated. Microcalorimetric titrations on model complexes suggested that the alpha-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 alpha-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.
author2 School of Physical and Mathematical Sciences
author_facet School of Physical and Mathematical Sciences
Dichtel, William R.
Zhao, Yanli
Trabolsi, Ali
Saha, Sourav
Aprahamian, Ivan
Stoddart, J. Fraser
format Article
author Dichtel, William R.
Zhao, Yanli
Trabolsi, Ali
Saha, Sourav
Aprahamian, Ivan
Stoddart, J. Fraser
author_sort Dichtel, William R.
title A redox-switchable α-cyclodextrin-based [2]rotaxane
title_short A redox-switchable α-cyclodextrin-based [2]rotaxane
title_full A redox-switchable α-cyclodextrin-based [2]rotaxane
title_fullStr A redox-switchable α-cyclodextrin-based [2]rotaxane
title_full_unstemmed A redox-switchable α-cyclodextrin-based [2]rotaxane
title_sort redox-switchable α-cyclodextrin-based [2]rotaxane
publishDate 2011
url https://hdl.handle.net/10356/92174
http://hdl.handle.net/10220/7042
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