Multistate Photoswitches:  Macrocyclic Dihydroazulene/Azobenzene Conjugates

Alexandru Vlasceanu; Mads Koerstz Madsen; Anders Bo Skov; Kurt Valentin Mikkelsen; Mogens Brøndsted Nielsen

doi:10.1002/anie.201712942

Multistate Photoswitches: Macrocyclic Dihydroazulene/Azobenzene Conjugates

Alexandru Vlasceanu, Mads Koerstz Madsen, Anders Bo Skov, Kurt Valentin Mikkelsen, Mogens Brøndsted Nielsen

Department of Chemistry

17 Citations (Scopus)

Abstract

Molecules comprised of three covalently linked bi-stable switches can exist in states described by a combination of binary numbers, one for each individual switch: ⟨000⟩, ⟨001⟩, etc. Here we have linked three photo-/thermoswitches together in a rigid macrocyclic structure, one azobenzene (bit no 1) and two dihydroazulenes (DHAs; bits no 2 and 3) and demonstrate how electronic interactions and unfavorable strain in some states can be used to control the speed by which a certain state is reached. More specifically, upon irradiation of state ⟨000⟩, the AZB isomerizes from trans to cis and the two DHAs to vinylheptafulvenes (VHFs), generating ⟨111⟩. The thermal VHF-to-DHA back-reactions from this state also occur stepwise and can be accelerated by photo-induced AZB cis-to-trans conversion, proceeding via ⟨011⟩ to ultimately furnish ⟨000⟩. Overall, the accessibility to a specific state of one bit was found to depend on the states of its neighboring bits.

Original language	English
Journal	Angewandte Chemie International Edition
Volume	57
Issue number	21
Pages (from-to)	6069-6072
Number of pages	4
ISSN	1433-7851
DOIs	https://doi.org/10.1002/anie.201712942
Publication status	Published - 22 May 2018

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@article{498fd84be6854130b5931e276943856d,

title = "Multistate Photoswitches: Macrocyclic Dihydroazulene/Azobenzene Conjugates",

abstract = "Molecules comprised of three covalently linked bi-stable switches can exist in states described by a combination of binary numbers, one for each individual switch: ⟨000⟩, ⟨001⟩, etc. Here we have linked three photo-/thermoswitches together in a rigid macrocyclic structure, one azobenzene (bit no 1) and two dihydroazulenes (DHAs; bits no 2 and 3) and demonstrate how electronic interactions and unfavorable strain in some states can be used to control the speed by which a certain state is reached. More specifically, upon irradiation of state ⟨000⟩, the AZB isomerizes from trans to cis and the two DHAs to vinylheptafulvenes (VHFs), generating ⟨111⟩. The thermal VHF-to-DHA back-reactions from this state also occur stepwise and can be accelerated by photo-induced AZB cis-to-trans conversion, proceeding via ⟨011⟩ to ultimately furnish ⟨000⟩. Overall, the accessibility to a specific state of one bit was found to depend on the states of its neighboring bits.",

author = "Alexandru Vlasceanu and Madsen, {Mads Koerstz} and Skov, {Anders Bo} and Mikkelsen, {Kurt Valentin} and Nielsen, {Mogens Br{\o}ndsted}",

year = "2018",

month = may,

day = "22",

doi = "10.1002/anie.201712942",

language = "English",

volume = "57",

pages = "6069--6072",

journal = "Angewandte Chemie International Edition",

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TY - JOUR

T1 - Multistate Photoswitches

T2 - Macrocyclic Dihydroazulene/Azobenzene Conjugates

AU - Vlasceanu, Alexandru

AU - Madsen, Mads Koerstz

AU - Skov, Anders Bo

AU - Mikkelsen, Kurt Valentin

AU - Nielsen, Mogens Brøndsted

PY - 2018/5/22

Y1 - 2018/5/22

N2 - Molecules comprised of three covalently linked bi-stable switches can exist in states described by a combination of binary numbers, one for each individual switch: ⟨000⟩, ⟨001⟩, etc. Here we have linked three photo-/thermoswitches together in a rigid macrocyclic structure, one azobenzene (bit no 1) and two dihydroazulenes (DHAs; bits no 2 and 3) and demonstrate how electronic interactions and unfavorable strain in some states can be used to control the speed by which a certain state is reached. More specifically, upon irradiation of state ⟨000⟩, the AZB isomerizes from trans to cis and the two DHAs to vinylheptafulvenes (VHFs), generating ⟨111⟩. The thermal VHF-to-DHA back-reactions from this state also occur stepwise and can be accelerated by photo-induced AZB cis-to-trans conversion, proceeding via ⟨011⟩ to ultimately furnish ⟨000⟩. Overall, the accessibility to a specific state of one bit was found to depend on the states of its neighboring bits.

AB - Molecules comprised of three covalently linked bi-stable switches can exist in states described by a combination of binary numbers, one for each individual switch: ⟨000⟩, ⟨001⟩, etc. Here we have linked three photo-/thermoswitches together in a rigid macrocyclic structure, one azobenzene (bit no 1) and two dihydroazulenes (DHAs; bits no 2 and 3) and demonstrate how electronic interactions and unfavorable strain in some states can be used to control the speed by which a certain state is reached. More specifically, upon irradiation of state ⟨000⟩, the AZB isomerizes from trans to cis and the two DHAs to vinylheptafulvenes (VHFs), generating ⟨111⟩. The thermal VHF-to-DHA back-reactions from this state also occur stepwise and can be accelerated by photo-induced AZB cis-to-trans conversion, proceeding via ⟨011⟩ to ultimately furnish ⟨000⟩. Overall, the accessibility to a specific state of one bit was found to depend on the states of its neighboring bits.

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DO - 10.1002/anie.201712942

M3 - Journal article

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JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 21

ER -

Multistate Photoswitches: Macrocyclic Dihydroazulene/Azobenzene Conjugates

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