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

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

*Kontaktforfatter for dette arbejde

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

Resumé

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+.

OriginalsprogEngelsk
TidsskriftEuropean Journal of Organic Chemistry
Vol/bind2019
Udgave nummer31-32
Sider (fra-til)5532-5539
ISSN1434-193X
DOI
StatusUdgivet - 1. sep. 2019

Fingeraftryk

Rotaxanes
Oxidation
Paraquat
Molecules
dihydroazulene
Oxidation-Reduction
Protons
Decomposition

Citer dette

Kilde, Martin Drøhse ; Kristensen, Rikke ; Olsen, Gunnar ; Jeppesen, Jan O. ; Nielsen, Mogens Brøndsted. / Redox-Active Monopyrrolotetrathiafulvalene-Based Rotaxane Incorporating the Dihydroazulene/Vinylheptafulvene Photo/Thermoswitch. I: European Journal of Organic Chemistry. 2019 ; Bind 2019, Nr. 31-32. s. 5532-5539.
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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+.",
keywords = "Heterocycles, Host–guest systems, Photochromism, Redox chemistry, Rotaxanes",
author = "Kilde, {Martin Dr{\o}hse} and Rikke Kristensen and Gunnar Olsen and Jeppesen, {Jan O.} and Nielsen, {Mogens Br{\o}ndsted}",
note = "Online Version of Record before inclusion in an issue. This article also appears in: Heterocyclic Chemistry",
year = "2019",
month = "9",
day = "1",
doi = "10.1002/ejoc.201900690",
language = "English",
volume = "2019",
pages = "5532--5539",
journal = "European Journal of Organic Chemistry",
issn = "1434-193X",
publisher = "Wiley - V C H Verlag GmbH & Co. KGaA",
number = "31-32",

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Redox-Active Monopyrrolotetrathiafulvalene-Based Rotaxane Incorporating the Dihydroazulene/Vinylheptafulvene Photo/Thermoswitch. / Kilde, Martin Drøhse; Kristensen, Rikke; Olsen, Gunnar; Jeppesen, Jan O.; Nielsen, Mogens Brøndsted.

I: European Journal of Organic Chemistry, Bind 2019, Nr. 31-32, 01.09.2019, s. 5532-5539.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Redox-Active Monopyrrolotetrathiafulvalene-Based Rotaxane Incorporating the Dihydroazulene/Vinylheptafulvene Photo/Thermoswitch

AU - Kilde, Martin Drøhse

AU - Kristensen, Rikke

AU - Olsen, Gunnar

AU - Jeppesen, Jan O.

AU - Nielsen, Mogens Brøndsted

N1 - Online Version of Record before inclusion in an issue. This article also appears in: Heterocyclic Chemistry

PY - 2019/9/1

Y1 - 2019/9/1

N2 - 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+.

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+.

KW - Heterocycles

KW - Host–guest systems

KW - Photochromism

KW - Redox chemistry

KW - Rotaxanes

U2 - 10.1002/ejoc.201900690

DO - 10.1002/ejoc.201900690

M3 - Journal article

VL - 2019

SP - 5532

EP - 5539

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

SN - 1434-193X

IS - 31-32

ER -