Comparison of linear and cross-conjugation from rates of vinylheptafulvene ring-closure

Kasper Fjelbye; Trine Nørgaard Christensen; Martyn Jevric; Søren Lindbæk Broman; Anne Ugleholdt Petersen; Anders Kadziola; Mogens Brøndsted Nielsen

doi:10.1002/ejoc.201403117

Comparison of linear and cross-conjugation from rates of vinylheptafulvene ring-closure

Kasper Fjelbye, Trine Nørgaard Christensen, Martyn Jevric, Søren Lindbæk Broman, Anne Ugleholdt Petersen, Anders Kadziola, Mogens Brøndsted Nielsen

Department of Chemistry

4 Citations (Scopus)

Abstract

The concept of cross-conjugation has in recent years attracted increasing interest in materials science as well as in the field of molecular electronics as a means to tune the optical properties and molecular conductance of nanoscale devices. In this paper we show how the rate of an electrocyclic reaction, the conversion of vinylheptafulvene (VHF) into dihydroazulene (DHA), is influenced by an electron-withdrawing p-nitrophenyl group separated from the VHF by either cross-conjugated or linearly π-conjugated bridging units. A selection of DHA/VHF molecules with ethyne, 1,1-and 1,2-diethynylethene, and 1,3-butadiyne bridges was prepared by metal-catalyzed coupling reactions. The effect of the different conjugated spacers on the kinetics of the conversion of VHF into DHA was examined by UV/Vis absorption spectroscopy by monitoring the decay of the VHF absorption. The cross-conjugated diethynylethene spacer was found to increase the half-life of the VHF relative to the linearly conjugated spacers.

Original language	English
Journal	European Journal of Organic Chemistry
Volume	2014
Issue number	35
Pages (from-to)	7859–7864
Number of pages	6
ISSN	1434-193X
DOIs	https://doi.org/10.1002/ejoc.201403117
Publication status	Published - 29 Oct 2014

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title = "Comparison of linear and cross-conjugation from rates of vinylheptafulvene ring-closure",

abstract = "The concept of cross-conjugation has in recent years attracted increasing interest in materials science as well as in the field of molecular electronics as a means to tune the optical properties and molecular conductance of nanoscale devices. In this paper we show how the rate of an electrocyclic reaction, the conversion of vinylheptafulvene (VHF) into dihydroazulene (DHA), is influenced by an electron-withdrawing p-nitrophenyl group separated from the VHF by either cross-conjugated or linearly π-conjugated bridging units. A selection of DHA/VHF molecules with ethyne, 1,1-and 1,2-diethynylethene, and 1,3-butadiyne bridges was prepared by metal-catalyzed coupling reactions. The effect of the different conjugated spacers on the kinetics of the conversion of VHF into DHA was examined by UV/Vis absorption spectroscopy by monitoring the decay of the VHF absorption. The cross-conjugated diethynylethene spacer was found to increase the half-life of the VHF relative to the linearly conjugated spacers.",

author = "Kasper Fjelbye and Christensen, {Trine N{\o}rgaard} and Martyn Jevric and Broman, {S{\o}ren Lindb{\ae}k} and Petersen, {Anne Ugleholdt} and Anders Kadziola and Nielsen, {Mogens Br{\o}ndsted}",

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language = "English",

volume = "2014",

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T1 - Comparison of linear and cross-conjugation from rates of vinylheptafulvene ring-closure

AU - Fjelbye, Kasper

AU - Christensen, Trine Nørgaard

AU - Jevric, Martyn

AU - Broman, Søren Lindbæk

AU - Petersen, Anne Ugleholdt

AU - Kadziola, Anders

AU - Nielsen, Mogens Brøndsted

PY - 2014/10/29

Y1 - 2014/10/29

N2 - The concept of cross-conjugation has in recent years attracted increasing interest in materials science as well as in the field of molecular electronics as a means to tune the optical properties and molecular conductance of nanoscale devices. In this paper we show how the rate of an electrocyclic reaction, the conversion of vinylheptafulvene (VHF) into dihydroazulene (DHA), is influenced by an electron-withdrawing p-nitrophenyl group separated from the VHF by either cross-conjugated or linearly π-conjugated bridging units. A selection of DHA/VHF molecules with ethyne, 1,1-and 1,2-diethynylethene, and 1,3-butadiyne bridges was prepared by metal-catalyzed coupling reactions. The effect of the different conjugated spacers on the kinetics of the conversion of VHF into DHA was examined by UV/Vis absorption spectroscopy by monitoring the decay of the VHF absorption. The cross-conjugated diethynylethene spacer was found to increase the half-life of the VHF relative to the linearly conjugated spacers.

AB - The concept of cross-conjugation has in recent years attracted increasing interest in materials science as well as in the field of molecular electronics as a means to tune the optical properties and molecular conductance of nanoscale devices. In this paper we show how the rate of an electrocyclic reaction, the conversion of vinylheptafulvene (VHF) into dihydroazulene (DHA), is influenced by an electron-withdrawing p-nitrophenyl group separated from the VHF by either cross-conjugated or linearly π-conjugated bridging units. A selection of DHA/VHF molecules with ethyne, 1,1-and 1,2-diethynylethene, and 1,3-butadiyne bridges was prepared by metal-catalyzed coupling reactions. The effect of the different conjugated spacers on the kinetics of the conversion of VHF into DHA was examined by UV/Vis absorption spectroscopy by monitoring the decay of the VHF absorption. The cross-conjugated diethynylethene spacer was found to increase the half-life of the VHF relative to the linearly conjugated spacers.

U2 - 10.1002/ejoc.201403117

DO - 10.1002/ejoc.201403117

M3 - Journal article

SN - 1434-193X

VL - 2014

SP - 7859

EP - 7864

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

IS - 35

ER -

Comparison of linear and cross-conjugation from rates of vinylheptafulvene ring-closure

Abstract

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