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

Kemisk Institut

3 Citationer (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⁺.

Originalsprog	Engelsk
Tidsskrift	European Journal of Organic Chemistry
Vol/bind	2019
Udgave nummer	31-32
Sider (fra-til)	5532-5539
Antal sider	8
ISSN	1434-193X
DOI	https://doi.org/10.1002/ejoc.201900690
Status	Udgivet - 1 sep. 2019

Adgang til dokumentet

10.1002/ejoc.201900690

Citationsformater

@article{aea0c99c170b438188f73623edeb692a,

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}",

year = "2019",

month = sep,

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",

}

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

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+.

U2 - 10.1002/ejoc.201900690

DO - 10.1002/ejoc.201900690

M3 - Journal article

SN - 1434-193X

VL - 2019

SP - 5532

EP - 5539

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

IS - 31-32

ER -

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

Abstract

Adgang til dokumentet

Fingeraftryk

Citationsformater