Functionalization at C(1) of the Dihydroazulene/Vinylheptafulvene Photo-/Thermoswitch - Establishing Structure−Property Relationship

Dianna Andersen; Martin Drøhse Kilde; Anders Kadziola; Martina Cacciarini; Mogens Brøndsted Nielsen

doi:10.1002/hlca.v101.11

Functionalization at C(1) of the Dihydroazulene/Vinylheptafulvene Photo-/Thermoswitch - Establishing Structure−Property Relationship

Dianna Andersen, Martin Drøhse Kilde, Anders Kadziola, Martina Cacciarini, Mogens Brøndsted Nielsen

Department of Chemistry

2 Citations (Scopus)

Abstract

The optical and switching properties of the dihydroazulene/vinylheptafulvene (DHA/VHF) photo-/thermoswitch can be finely tuned by substituent groups at specific positions. While the kinetics of the thermal ring closure of VHF into DHA have previously been shown to follow systematic trends in regard to the electron-withdrawing/donating character of substituents at DHA positions C(2), C(3), and C(7) (Hammett correlations), no such correlation has so far been established for a selection of compounds with different substituents at C(1). Functionalization at this position is at the same time known to have the strongest impact on the VHF-to-DHA conversion rate. Here we show that introduction of a benzothiazole ring at C(1) of DHA (corresponding to the vinyl position of VHF) with various electron-withdrawing/donating groups provides VHFs whose rates of ring closure follow a Hammett correlation – the more electron-withdrawing substituent on the benzothiazole, the faster ring closure reaction.

Original language	English
Article number	e1800153
Journal	Helvetica Chimica Acta
Volume	101
Issue number	11
Pages (from-to)	1-9
Number of pages	9
ISSN	0018-019X
DOIs	https://doi.org/10.1002/hlca.v101.11
Publication status	Published - Nov 2018

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title = "Functionalization at C(1) of the Dihydroazulene/Vinylheptafulvene Photo-/Thermoswitch - Establishing Structure−Property Relationship",

abstract = "The optical and switching properties of the dihydroazulene/vinylheptafulvene (DHA/VHF) photo-/thermoswitch can be finely tuned by substituent groups at specific positions. While the kinetics of the thermal ring closure of VHF into DHA have previously been shown to follow systematic trends in regard to the electron-withdrawing/donating character of substituents at DHA positions C(2), C(3), and C(7) (Hammett correlations), no such correlation has so far been established for a selection of compounds with different substituents at C(1). Functionalization at this position is at the same time known to have the strongest impact on the VHF-to-DHA conversion rate. Here we show that introduction of a benzothiazole ring at C(1) of DHA (corresponding to the vinyl position of VHF) with various electron-withdrawing/donating groups provides VHFs whose rates of ring closure follow a Hammett correlation – the more electron-withdrawing substituent on the benzothiazole, the faster ring closure reaction.",

author = "Dianna Andersen and Martin Dr{\o}hse Kilde and Anders Kadziola and Martina Cacciarini and Mogens Br{\o}ndsted Nielsen",

year = "2018",

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T1 - Functionalization at C(1) of the Dihydroazulene/Vinylheptafulvene Photo-/Thermoswitch - Establishing Structure−Property Relationship

AU - Andersen, Dianna

AU - Drøhse Kilde, Martin

AU - Kadziola, Anders

AU - Cacciarini, Martina

AU - Brøndsted Nielsen, Mogens

PY - 2018/11

Y1 - 2018/11

N2 - The optical and switching properties of the dihydroazulene/vinylheptafulvene (DHA/VHF) photo-/thermoswitch can be finely tuned by substituent groups at specific positions. While the kinetics of the thermal ring closure of VHF into DHA have previously been shown to follow systematic trends in regard to the electron-withdrawing/donating character of substituents at DHA positions C(2), C(3), and C(7) (Hammett correlations), no such correlation has so far been established for a selection of compounds with different substituents at C(1). Functionalization at this position is at the same time known to have the strongest impact on the VHF-to-DHA conversion rate. Here we show that introduction of a benzothiazole ring at C(1) of DHA (corresponding to the vinyl position of VHF) with various electron-withdrawing/donating groups provides VHFs whose rates of ring closure follow a Hammett correlation – the more electron-withdrawing substituent on the benzothiazole, the faster ring closure reaction.

AB - The optical and switching properties of the dihydroazulene/vinylheptafulvene (DHA/VHF) photo-/thermoswitch can be finely tuned by substituent groups at specific positions. While the kinetics of the thermal ring closure of VHF into DHA have previously been shown to follow systematic trends in regard to the electron-withdrawing/donating character of substituents at DHA positions C(2), C(3), and C(7) (Hammett correlations), no such correlation has so far been established for a selection of compounds with different substituents at C(1). Functionalization at this position is at the same time known to have the strongest impact on the VHF-to-DHA conversion rate. Here we show that introduction of a benzothiazole ring at C(1) of DHA (corresponding to the vinyl position of VHF) with various electron-withdrawing/donating groups provides VHFs whose rates of ring closure follow a Hammett correlation – the more electron-withdrawing substituent on the benzothiazole, the faster ring closure reaction.

U2 - 10.1002/hlca.v101.11

DO - 10.1002/hlca.v101.11

M3 - Journal article

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VL - 101

SP - 1

EP - 9

JO - Helvetica Chimica Acta

JF - Helvetica Chimica Acta

IS - 11

M1 - e1800153

ER -

Functionalization at C(1) of the Dihydroazulene/Vinylheptafulvene Photo-/Thermoswitch - Establishing Structure−Property Relationship

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