Dialkylated Dihydroazulene and Vinylheptafulvene Derivatives - Synthesis and Switching Properties

Nickie C. M. Lubrin; Alexandru Vlasceanu; Benjamin N. Frandsen; Anders Bo Skov; Martin Drøhse Kilde; Kurt Valentin Mikkelsen; Mogens Brøndsted Nielsen

doi:10.1002/ejoc.201700446

Dialkylated Dihydroazulene and Vinylheptafulvene Derivatives - Synthesis and Switching Properties

Nickie C. M. Lubrin, Alexandru Vlasceanu, Benjamin N. Frandsen, Anders Bo Skov, Martin Drøhse Kilde, Kurt Valentin Mikkelsen, Mogens Brøndsted Nielsen

Department of Chemistry

6 Citations (Scopus)

Abstract

Functionalization of molecular photoswitches at specific positions offers a way of tuning their switching properties. The work presented here describes the development of a new protocol towards the synthesis and functionalization of the dihydroazulene/vinylheptafulvene (DHA/VHF) photo-/thermoswitch. The key step is a facile condensation reaction using a functionalized tropone derivative, and the new synthetic method was employed in the regioselective preparation of a novel dimethyl-substituted DHA photoswitch. This compound presents the first accessible derivative with alkyl groups on the seven-membered ring of the system ― at positions C5 and C7. From experimental and theoretical kinetics studies on the thermal VHF-to-DHA electrocyclic reaction, the influence of the electron-donating methyl groups was elucidated. In addition, we subjected a small selection of 4,8a-dialkylated compounds to a computational study to elucidate how steric interactions can alter the relative DHA–VHF stabilities. The synthetic methodology offers access to novel DHA scaffolds and substitution patterns, which in turn can lead to systems that can help to address broader questions concerning the potential applicability of the DHA/VHF system in the context of solar-thermal energy-storage systems or other photochromic applications.

Original language	English
Journal	European Journal of Organic Chemistry
Volume	20
Pages (from-to)	2932-2939
Number of pages	8
ISSN	1434-193X
DOIs	https://doi.org/10.1002/ejoc.201700446
Publication status	Published - 26 May 2017

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@article{8d762ffebd68497186b2044828b25042,

title = "Dialkylated Dihydroazulene and Vinylheptafulvene Derivatives - Synthesis and Switching Properties",

abstract = "Functionalization of molecular photoswitches at specific positions offers a way of tuning their switching properties. The work presented here describes the development of a new protocol towards the synthesis and functionalization of the dihydroazulene/vinylheptafulvene (DHA/VHF) photo-/thermoswitch. The key step is a facile condensation reaction using a functionalized tropone derivative, and the new synthetic method was employed in the regioselective preparation of a novel dimethyl-substituted DHA photoswitch. This compound presents the first accessible derivative with alkyl groups on the seven-membered ring of the system ― at positions C5 and C7. From experimental and theoretical kinetics studies on the thermal VHF-to-DHA electrocyclic reaction, the influence of the electron-donating methyl groups was elucidated. In addition, we subjected a small selection of 4,8a-dialkylated compounds to a computational study to elucidate how steric interactions can alter the relative DHA–VHF stabilities. The synthetic methodology offers access to novel DHA scaffolds and substitution patterns, which in turn can lead to systems that can help to address broader questions concerning the potential applicability of the DHA/VHF system in the context of solar-thermal energy-storage systems or other photochromic applications.",

author = "Lubrin, {Nickie C. M.} and Alexandru Vlasceanu and Frandsen, {Benjamin N.} and Skov, {Anders Bo} and Kilde, {Martin Dr{\o}hse} and Mikkelsen, {Kurt Valentin} and Nielsen, {Mogens Br{\o}ndsted}",

year = "2017",

month = may,

day = "26",

doi = "10.1002/ejoc.201700446",

language = "English",

volume = "20",

pages = "2932--2939",

journal = "European Journal of Organic Chemistry",

issn = "1434-193X",

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T1 - Dialkylated Dihydroazulene and Vinylheptafulvene Derivatives - Synthesis and Switching Properties

AU - Lubrin, Nickie C. M.

AU - Vlasceanu, Alexandru

AU - Frandsen, Benjamin N.

AU - Skov, Anders Bo

AU - Kilde, Martin Drøhse

AU - Mikkelsen, Kurt Valentin

AU - Nielsen, Mogens Brøndsted

PY - 2017/5/26

Y1 - 2017/5/26

N2 - Functionalization of molecular photoswitches at specific positions offers a way of tuning their switching properties. The work presented here describes the development of a new protocol towards the synthesis and functionalization of the dihydroazulene/vinylheptafulvene (DHA/VHF) photo-/thermoswitch. The key step is a facile condensation reaction using a functionalized tropone derivative, and the new synthetic method was employed in the regioselective preparation of a novel dimethyl-substituted DHA photoswitch. This compound presents the first accessible derivative with alkyl groups on the seven-membered ring of the system ― at positions C5 and C7. From experimental and theoretical kinetics studies on the thermal VHF-to-DHA electrocyclic reaction, the influence of the electron-donating methyl groups was elucidated. In addition, we subjected a small selection of 4,8a-dialkylated compounds to a computational study to elucidate how steric interactions can alter the relative DHA–VHF stabilities. The synthetic methodology offers access to novel DHA scaffolds and substitution patterns, which in turn can lead to systems that can help to address broader questions concerning the potential applicability of the DHA/VHF system in the context of solar-thermal energy-storage systems or other photochromic applications.

AB - Functionalization of molecular photoswitches at specific positions offers a way of tuning their switching properties. The work presented here describes the development of a new protocol towards the synthesis and functionalization of the dihydroazulene/vinylheptafulvene (DHA/VHF) photo-/thermoswitch. The key step is a facile condensation reaction using a functionalized tropone derivative, and the new synthetic method was employed in the regioselective preparation of a novel dimethyl-substituted DHA photoswitch. This compound presents the first accessible derivative with alkyl groups on the seven-membered ring of the system ― at positions C5 and C7. From experimental and theoretical kinetics studies on the thermal VHF-to-DHA electrocyclic reaction, the influence of the electron-donating methyl groups was elucidated. In addition, we subjected a small selection of 4,8a-dialkylated compounds to a computational study to elucidate how steric interactions can alter the relative DHA–VHF stabilities. The synthetic methodology offers access to novel DHA scaffolds and substitution patterns, which in turn can lead to systems that can help to address broader questions concerning the potential applicability of the DHA/VHF system in the context of solar-thermal energy-storage systems or other photochromic applications.

U2 - 10.1002/ejoc.201700446

DO - 10.1002/ejoc.201700446

M3 - Journal article

SN - 1434-193X

VL - 20

SP - 2932

EP - 2939

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

ER -

Dialkylated Dihydroazulene and Vinylheptafulvene Derivatives - Synthesis and Switching Properties

Abstract

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