Density Functional Theory Study of Carbamoyl-Substituted Dihydroazulene/Vinylheptafulvene Derivatives and Solvent Effects

Oliver Christensen; Lauge E. Nielsen; Jes Johansen; Karin Holk; Jonas Udmark; Mogens Brøndsted Nielsen; Martina Cacciarini; Kurt V. Mikkelsen

doi:10.1021/acs.jpcc.2c00490

Density Functional Theory Study of Carbamoyl-Substituted Dihydroazulene/Vinylheptafulvene Derivatives and Solvent Effects

Oliver Christensen, Lauge E. Nielsen, Jes Johansen, Karin Holk, Jonas Udmark, Mogens Brøndsted Nielsen, Martina Cacciarini, Kurt V. Mikkelsen^*

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Journal article › Research › peer-review

1 Citation (Scopus)

Abstract

Systematic functionalization of the dihydroazulene (DHA)/vinylheptafulvene (VHF) photo/thermoswitch allows for tuning of the thermochemical and optical properties of the system, which is of particular relevance for improving its capabilities as a solar energy storage and release system. Using a computational chemistry approach, this work investigates the thermochemical and optical properties of several different DHA/VHF systems bearing on position C1 of DHA amide or ester electron-acceptor groups. Solvent effects were investigated using a polarizable dielectric medium model for the solvents cyclohexane, toluene, dichloromethane, ethanol, and acetonitrile along with calculations in vacuum. All systems show increased energy storage density compared to the 1,1-dicyano parent system, with generally lower activation barriers for the VHF-to-DHA back-conversion across all solvents. Increasing solvent polarity led to a calculated redshift of the absorption spectra and an increase in intensities for all systems, with values comparable to the parent reference in vacuo and redshifted by around 15 nm in acetonitrile for some compounds. Experimental kinetic studies for the VHF-to-DHA conversion were performed and compared to the computational findings.

Original language	English
Journal	Journal of Physical Chemistry C
Volume	126
Issue number	10
Pages (from-to)	4815-4825
Number of pages	11
ISSN	1932-7447
DOIs	https://doi.org/10.1021/acs.jpcc.2c00490
Publication status	Published - 2022

Bibliographical note

Funding Information:
This work was supported by the Center for Exploitation of Solar Energy, Department of Chemistry, University of Copenhagen, Denmark and the Danish e-Infrastructure Cooperation. MIUR − progetto Dipartimenti di Eccellenza 2018−2022 (ref. B96C1700020008) is acknowledged for financial support.

Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.

Access to Document

10.1021/acs.jpcc.2c00490

Cite this

Density Functional Theory Study of Carbamoyl-Substituted Dihydroazulene/Vinylheptafulvene Derivatives and Solvent Effects. / Christensen, Oliver; Nielsen, Lauge E.; Johansen, Jes; Holk, Karin; Udmark, Jonas; Nielsen, Mogens Brøndsted ; Cacciarini, Martina ; Mikkelsen, Kurt V.

In: Journal of Physical Chemistry C, Vol. 126, No. 10, 2022, p. 4815-4825.

Research output: Contribution to journal › Journal article › Research › peer-review

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title = "Density Functional Theory Study of Carbamoyl-Substituted Dihydroazulene/Vinylheptafulvene Derivatives and Solvent Effects",

abstract = "Systematic functionalization of the dihydroazulene (DHA)/vinylheptafulvene (VHF) photo/thermoswitch allows for tuning of the thermochemical and optical properties of the system, which is of particular relevance for improving its capabilities as a solar energy storage and release system. Using a computational chemistry approach, this work investigates the thermochemical and optical properties of several different DHA/VHF systems bearing on position C1 of DHA amide or ester electron-acceptor groups. Solvent effects were investigated using a polarizable dielectric medium model for the solvents cyclohexane, toluene, dichloromethane, ethanol, and acetonitrile along with calculations in vacuum. All systems show increased energy storage density compared to the 1,1-dicyano parent system, with generally lower activation barriers for the VHF-to-DHA back-conversion across all solvents. Increasing solvent polarity led to a calculated redshift of the absorption spectra and an increase in intensities for all systems, with values comparable to the parent reference in vacuo and redshifted by around 15 nm in acetonitrile for some compounds. Experimental kinetic studies for the VHF-to-DHA conversion were performed and compared to the computational findings.",

author = "Oliver Christensen and Nielsen, {Lauge E.} and Jes Johansen and Karin Holk and Jonas Udmark and Nielsen, {Mogens Br{\o}ndsted} and Martina Cacciarini and Mikkelsen, {Kurt V.}",

note = "Funding Information: This work was supported by the Center for Exploitation of Solar Energy, Department of Chemistry, University of Copenhagen, Denmark and the Danish e-Infrastructure Cooperation. MIUR − progetto Dipartimenti di Eccellenza 2018−2022 (ref. B96C1700020008) is acknowledged for financial support. Publisher Copyright: {\textcopyright} 2022 American Chemical Society. All rights reserved.",

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AU - Mikkelsen, Kurt V.

N1 - Funding Information: This work was supported by the Center for Exploitation of Solar Energy, Department of Chemistry, University of Copenhagen, Denmark and the Danish e-Infrastructure Cooperation. MIUR − progetto Dipartimenti di Eccellenza 2018−2022 (ref. B96C1700020008) is acknowledged for financial support. Publisher Copyright: © 2022 American Chemical Society. All rights reserved.

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N2 - Systematic functionalization of the dihydroazulene (DHA)/vinylheptafulvene (VHF) photo/thermoswitch allows for tuning of the thermochemical and optical properties of the system, which is of particular relevance for improving its capabilities as a solar energy storage and release system. Using a computational chemistry approach, this work investigates the thermochemical and optical properties of several different DHA/VHF systems bearing on position C1 of DHA amide or ester electron-acceptor groups. Solvent effects were investigated using a polarizable dielectric medium model for the solvents cyclohexane, toluene, dichloromethane, ethanol, and acetonitrile along with calculations in vacuum. All systems show increased energy storage density compared to the 1,1-dicyano parent system, with generally lower activation barriers for the VHF-to-DHA back-conversion across all solvents. Increasing solvent polarity led to a calculated redshift of the absorption spectra and an increase in intensities for all systems, with values comparable to the parent reference in vacuo and redshifted by around 15 nm in acetonitrile for some compounds. Experimental kinetic studies for the VHF-to-DHA conversion were performed and compared to the computational findings.

AB - Systematic functionalization of the dihydroazulene (DHA)/vinylheptafulvene (VHF) photo/thermoswitch allows for tuning of the thermochemical and optical properties of the system, which is of particular relevance for improving its capabilities as a solar energy storage and release system. Using a computational chemistry approach, this work investigates the thermochemical and optical properties of several different DHA/VHF systems bearing on position C1 of DHA amide or ester electron-acceptor groups. Solvent effects were investigated using a polarizable dielectric medium model for the solvents cyclohexane, toluene, dichloromethane, ethanol, and acetonitrile along with calculations in vacuum. All systems show increased energy storage density compared to the 1,1-dicyano parent system, with generally lower activation barriers for the VHF-to-DHA back-conversion across all solvents. Increasing solvent polarity led to a calculated redshift of the absorption spectra and an increase in intensities for all systems, with values comparable to the parent reference in vacuo and redshifted by around 15 nm in acetonitrile for some compounds. Experimental kinetic studies for the VHF-to-DHA conversion were performed and compared to the computational findings.

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