Excited State Charge Separation in an Azobenzene-Bridged Perylenediimide Dimer – Effect of Photochemical Trans-Cis Isomerization

Photoinduced charge transfer and separation events in a newly synthesized azobenzene-bridged perylenediimide-dimer (PDI-dimer) are demonstrated. Trans-to-cis conversion (∼50 % efficiency) from the initial trans PDI-dimer by 355 nm pulsed laser light, and its reversal, cis-to-trans, process by 435 nm...

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Autores: Zink Lorre, Nathalie, Seetharaman, Sairaman, Gutiérrez Moreno, David, Fernández-Lázaro, Fernando, Karr, Paul A., D’Souza, Francis
Tipo de recurso: artículo
Fecha de publicación:2021
País:España
Institución:Universidad Miguel Hernández de Elche
Repositorio:REDIUMH. Depósito Digital de la UMH
OAI Identifier:oai:dspace.umh.es:11000/31033
Acceso en línea:https://hdl.handle.net/11000/31033
Access Level:acceso abierto
Palabra clave:azobenzene
excited state charge transfer
perylenediimide dimer
symmetry breaking
trans-cis isomerization
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spelling Excited State Charge Separation in an Azobenzene-Bridged Perylenediimide Dimer – Effect of Photochemical Trans-Cis IsomerizationZink Lorre, NathalieSeetharaman, SairamanGutiérrez Moreno, DavidFernández-Lázaro, FernandoKarr, Paul A.D’Souza, Francisazobenzeneexcited state charge transferperylenediimide dimersymmetry breakingtrans-cis isomerizationPhotoinduced charge transfer and separation events in a newly synthesized azobenzene-bridged perylenediimide-dimer (PDI-dimer) are demonstrated. Trans-to-cis conversion (∼50 % efficiency) from the initial trans PDI-dimer by 355 nm pulsed laser light, and its reversal, cis-to-trans, process by 435 nm laser light irradiation has been possible to accomplish. Efficient fluorescence quenching in the PDI-dimer, more so for the cis isomer was witnessed, and such quenching increased with increasing solvent polarity. DFT-calculated geometry and electronic structures helped in visualizing the charge transfer in the PDI-dimer in both isomeric forms, and also revealed certain degree of participation of the azobenzene entity in the charge transfer events. Femtosecond transient absorption spectral studies confirmed occurrence of both charge transfer followed by charge separation in the studied PDI-dimer in both trans and cis forms in polar solvents, and the evaluated time constants from Global target analysis revealed accelerated events in the cis PDI-dimer due to proximity effects. The present study offers key insights on the role of the azobenzene bridge, and the dimer geometry in governing the excited state charge transfer and separation in symmetrically linked PDI dimer.Wiley-VCH GmbHDepartamentos de la UMH::Farmacología, Pediatría y Química Orgánica202420242021info:eu-repo/semantics/articleapplication/pdf10application/pdfhttps://hdl.handle.net/11000/31033reponame:REDIUMH. Depósito Digital de la UMHinstname:Universidad Miguel Hernández de ElcheIngléshttps://doi.org/10.1002/chem.202102903info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-nd/4.0/oai:dspace.umh.es:11000/310332026-05-27T13:36:21Z
dc.title.none.fl_str_mv Excited State Charge Separation in an Azobenzene-Bridged Perylenediimide Dimer – Effect of Photochemical Trans-Cis Isomerization
title Excited State Charge Separation in an Azobenzene-Bridged Perylenediimide Dimer – Effect of Photochemical Trans-Cis Isomerization
spellingShingle Excited State Charge Separation in an Azobenzene-Bridged Perylenediimide Dimer – Effect of Photochemical Trans-Cis Isomerization
Zink Lorre, Nathalie
azobenzene
excited state charge transfer
perylenediimide dimer
symmetry breaking
trans-cis isomerization
title_short Excited State Charge Separation in an Azobenzene-Bridged Perylenediimide Dimer – Effect of Photochemical Trans-Cis Isomerization
title_full Excited State Charge Separation in an Azobenzene-Bridged Perylenediimide Dimer – Effect of Photochemical Trans-Cis Isomerization
title_fullStr Excited State Charge Separation in an Azobenzene-Bridged Perylenediimide Dimer – Effect of Photochemical Trans-Cis Isomerization
title_full_unstemmed Excited State Charge Separation in an Azobenzene-Bridged Perylenediimide Dimer – Effect of Photochemical Trans-Cis Isomerization
title_sort Excited State Charge Separation in an Azobenzene-Bridged Perylenediimide Dimer – Effect of Photochemical Trans-Cis Isomerization
dc.creator.none.fl_str_mv Zink Lorre, Nathalie
Seetharaman, Sairaman
Gutiérrez Moreno, David
Fernández-Lázaro, Fernando
Karr, Paul A.
D’Souza, Francis
author Zink Lorre, Nathalie
author_facet Zink Lorre, Nathalie
Seetharaman, Sairaman
Gutiérrez Moreno, David
Fernández-Lázaro, Fernando
Karr, Paul A.
D’Souza, Francis
author_role author
author2 Seetharaman, Sairaman
Gutiérrez Moreno, David
Fernández-Lázaro, Fernando
Karr, Paul A.
D’Souza, Francis
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Departamentos de la UMH::Farmacología, Pediatría y Química Orgánica
dc.subject.none.fl_str_mv azobenzene
excited state charge transfer
perylenediimide dimer
symmetry breaking
trans-cis isomerization
topic azobenzene
excited state charge transfer
perylenediimide dimer
symmetry breaking
trans-cis isomerization
description Photoinduced charge transfer and separation events in a newly synthesized azobenzene-bridged perylenediimide-dimer (PDI-dimer) are demonstrated. Trans-to-cis conversion (∼50 % efficiency) from the initial trans PDI-dimer by 355 nm pulsed laser light, and its reversal, cis-to-trans, process by 435 nm laser light irradiation has been possible to accomplish. Efficient fluorescence quenching in the PDI-dimer, more so for the cis isomer was witnessed, and such quenching increased with increasing solvent polarity. DFT-calculated geometry and electronic structures helped in visualizing the charge transfer in the PDI-dimer in both isomeric forms, and also revealed certain degree of participation of the azobenzene entity in the charge transfer events. Femtosecond transient absorption spectral studies confirmed occurrence of both charge transfer followed by charge separation in the studied PDI-dimer in both trans and cis forms in polar solvents, and the evaluated time constants from Global target analysis revealed accelerated events in the cis PDI-dimer due to proximity effects. The present study offers key insights on the role of the azobenzene bridge, and the dimer geometry in governing the excited state charge transfer and separation in symmetrically linked PDI dimer.
publishDate 2021
dc.date.none.fl_str_mv 2021
2024
2024
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/11000/31033
url https://hdl.handle.net/11000/31033
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv https://doi.org/10.1002/chem.202102903
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.format.none.fl_str_mv application/pdf
10
application/pdf
dc.publisher.none.fl_str_mv Wiley-VCH GmbH
publisher.none.fl_str_mv Wiley-VCH GmbH
dc.source.none.fl_str_mv reponame:REDIUMH. Depósito Digital de la UMH
instname:Universidad Miguel Hernández de Elche
instname_str Universidad Miguel Hernández de Elche
reponame_str REDIUMH. Depósito Digital de la UMH
collection REDIUMH. Depósito Digital de la UMH
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300724

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