Redox-Active Monopyrrolotetrathiafulvalene-Based Rotaxane Incorporating the Dihydroazulene/Vinylheptafulvene Photo/Thermoswitch

Martin Drøhse Kilde; Rikke Kristensen; Gunnar Olsen; Jan O. Jeppesen; Mogens Brøndsted Nielsen

doi:10.1002/ejoc.201900690

Redox-Active Monopyrrolotetrathiafulvalene-Based Rotaxane Incorporating the Dihydroazulene/Vinylheptafulvene Photo/Thermoswitch

Martin Drøhse Kilde, Rikke Kristensen, Gunnar Olsen, Jan O. Jeppesen, Mogens Brøndsted Nielsen

Department of Chemistry

3 Citations (Scopus)

Abstract

A dumbbell-shaped molecule with a central monopyrrolo-tetrathiafulvalene (MPTTF) unit and a 1,1-dicyano-dihydroazulene (DHA) photoswitch as one of the two end-groups was prepared and subsequently converted into a [2]rotaxane with cyclobis(paraquat-p-phenylene) (CBPQT⁴⁺) as the ring component. Investigations revealed that both the DHA and its vinylheptafulvene (VHF) photoisomer prevent deslipping of CBPQT⁴⁺. It was found that the presence of the CBPQT⁴⁺ ring on the MPTTF-DHA dumbbell changes the rate of the thermal back-conversion of VHF into DHA, i.e., this conversion was found to be accelerated by the presence of the positively charged CBPQT⁴⁺ ring. Studies also showed that DHA forms a weak complex with CBPQT⁴⁺, which seems to originate from weak interactions between the cyano group located on DHA and the bipyridinium α-protons on CBPQT⁴⁺. The rotaxane was subjected to various oxidation experiments, but these were, unfortunately, accompanied by some decomposition of the molecule; yet, movement of the CBPQT⁴⁺ ring from the MPTTF unit towards the DHA moiety seems to occur upon oxidation of the MPTTF unit, promoted by the weak interaction between the DHA moiety and CBPQT⁴⁺.

Original language	English
Journal	European Journal of Organic Chemistry
Volume	2019
Issue number	31-32
Pages (from-to)	5532-5539
Number of pages	8
ISSN	1434-193X
DOIs	https://doi.org/10.1002/ejoc.201900690
Publication status	Published - 1 Sept 2019

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Redox-Active Monopyrrolotetrathiafulvalene-Based Rotaxane Incorporating the Dihydroazulene/Vinylheptafulvene Photo/Thermoswitch. / Kilde, Martin Drøhse; Kristensen, Rikke; Olsen, Gunnar et al.
In: European Journal of Organic Chemistry, Vol. 2019, No. 31-32, 01.09.2019, p. 5532-5539.

Research output: Contribution to journal › Journal article › Research › peer-review

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title = "Redox-Active Monopyrrolotetrathiafulvalene-Based Rotaxane Incorporating the Dihydroazulene/Vinylheptafulvene Photo/Thermoswitch",

abstract = "A dumbbell-shaped molecule with a central monopyrrolo-tetrathiafulvalene (MPTTF) unit and a 1,1-dicyano-dihydroazulene (DHA) photoswitch as one of the two end-groups was prepared and subsequently converted into a [2]rotaxane with cyclobis(paraquat-p-phenylene) (CBPQT4+) as the ring component. Investigations revealed that both the DHA and its vinylheptafulvene (VHF) photoisomer prevent deslipping of CBPQT4+. It was found that the presence of the CBPQT4+ ring on the MPTTF-DHA dumbbell changes the rate of the thermal back-conversion of VHF into DHA, i.e., this conversion was found to be accelerated by the presence of the positively charged CBPQT4+ ring. Studies also showed that DHA forms a weak complex with CBPQT4+, which seems to originate from weak interactions between the cyano group located on DHA and the bipyridinium α-protons on CBPQT4+. The rotaxane was subjected to various oxidation experiments, but these were, unfortunately, accompanied by some decomposition of the molecule; yet, movement of the CBPQT4+ ring from the MPTTF unit towards the DHA moiety seems to occur upon oxidation of the MPTTF unit, promoted by the weak interaction between the DHA moiety and CBPQT4+.",

author = "Kilde, {Martin Dr{\o}hse} and Rikke Kristensen and Gunnar Olsen and Jeppesen, {Jan O.} and Nielsen, {Mogens Br{\o}ndsted}",

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AB - A dumbbell-shaped molecule with a central monopyrrolo-tetrathiafulvalene (MPTTF) unit and a 1,1-dicyano-dihydroazulene (DHA) photoswitch as one of the two end-groups was prepared and subsequently converted into a [2]rotaxane with cyclobis(paraquat-p-phenylene) (CBPQT4+) as the ring component. Investigations revealed that both the DHA and its vinylheptafulvene (VHF) photoisomer prevent deslipping of CBPQT4+. It was found that the presence of the CBPQT4+ ring on the MPTTF-DHA dumbbell changes the rate of the thermal back-conversion of VHF into DHA, i.e., this conversion was found to be accelerated by the presence of the positively charged CBPQT4+ ring. Studies also showed that DHA forms a weak complex with CBPQT4+, which seems to originate from weak interactions between the cyano group located on DHA and the bipyridinium α-protons on CBPQT4+. The rotaxane was subjected to various oxidation experiments, but these were, unfortunately, accompanied by some decomposition of the molecule; yet, movement of the CBPQT4+ ring from the MPTTF unit towards the DHA moiety seems to occur upon oxidation of the MPTTF unit, promoted by the weak interaction between the DHA moiety and CBPQT4+.

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DO - 10.1002/ejoc.201900690

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Redox-Active Monopyrrolotetrathiafulvalene-Based Rotaxane Incorporating the Dihydroazulene/Vinylheptafulvene Photo/Thermoswitch

Abstract

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