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All Visible Light Photoswitch Based on the Dimethyldihydropyrene Unit Operating in Aqueous Solutions with High Quantum Yields

[Image: see text] Molecular systems and devices whose properties can be modulated using light as an external stimulus are the subject of numerous research studies in the fields of materials and life sciences. In this context, the use of photochromic compounds that reversibly switch upon light irradi...

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Autores principales: Ziani, Zakaria, Cobo, Saioa, Loiseau, Frédérique, Jouvenot, Damien, Lognon, Elise, Boggio-Pasqua, Martial, Royal, Guy
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9875246/
https://www.ncbi.nlm.nih.gov/pubmed/36711101
http://dx.doi.org/10.1021/jacsau.2c00552
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author Ziani, Zakaria
Cobo, Saioa
Loiseau, Frédérique
Jouvenot, Damien
Lognon, Elise
Boggio-Pasqua, Martial
Royal, Guy
author_facet Ziani, Zakaria
Cobo, Saioa
Loiseau, Frédérique
Jouvenot, Damien
Lognon, Elise
Boggio-Pasqua, Martial
Royal, Guy
author_sort Ziani, Zakaria
collection PubMed
description [Image: see text] Molecular systems and devices whose properties can be modulated using light as an external stimulus are the subject of numerous research studies in the fields of materials and life sciences. In this context, the use of photochromic compounds that reversibly switch upon light irradiation is particularly attractive. However, for many envisioned applications, and in particular for biological purposes, illumination with harmful UV light must be avoided and these photoactivable systems must operate in aqueous media. In this context, we have designed a benzo[e]-fused dimethyldihydropyrene compound bearing a methyl-pyridinium electroacceptor group that meets these requirements. This compound (closed state) is able to reversibly isomerize under aerobic conditions into its corresponding cyclophanediene form (open isomer) through the opening of its central carbon–carbon bond. Both the photo-opening and the reverse photoclosing processes are triggered by visible light illumination and proceed with high quantum yields (respectively 14.5% yield at λ = 680 nm and quantitative quantum yield at λ = 470 nm, in water). This system has been investigated by nuclear magnetic resonance and absorption spectroscopy, and the efficient photoswitching behavior was rationalized by spin-flip time-dependent density functional theory calculations. In addition, it is demonstrated that the isomerization from the open to the closed form can be electrocatalytically triggered.
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spelling pubmed-98752462023-01-26 All Visible Light Photoswitch Based on the Dimethyldihydropyrene Unit Operating in Aqueous Solutions with High Quantum Yields Ziani, Zakaria Cobo, Saioa Loiseau, Frédérique Jouvenot, Damien Lognon, Elise Boggio-Pasqua, Martial Royal, Guy JACS Au [Image: see text] Molecular systems and devices whose properties can be modulated using light as an external stimulus are the subject of numerous research studies in the fields of materials and life sciences. In this context, the use of photochromic compounds that reversibly switch upon light irradiation is particularly attractive. However, for many envisioned applications, and in particular for biological purposes, illumination with harmful UV light must be avoided and these photoactivable systems must operate in aqueous media. In this context, we have designed a benzo[e]-fused dimethyldihydropyrene compound bearing a methyl-pyridinium electroacceptor group that meets these requirements. This compound (closed state) is able to reversibly isomerize under aerobic conditions into its corresponding cyclophanediene form (open isomer) through the opening of its central carbon–carbon bond. Both the photo-opening and the reverse photoclosing processes are triggered by visible light illumination and proceed with high quantum yields (respectively 14.5% yield at λ = 680 nm and quantitative quantum yield at λ = 470 nm, in water). This system has been investigated by nuclear magnetic resonance and absorption spectroscopy, and the efficient photoswitching behavior was rationalized by spin-flip time-dependent density functional theory calculations. In addition, it is demonstrated that the isomerization from the open to the closed form can be electrocatalytically triggered. American Chemical Society 2022-12-21 /pmc/articles/PMC9875246/ /pubmed/36711101 http://dx.doi.org/10.1021/jacsau.2c00552 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Ziani, Zakaria
Cobo, Saioa
Loiseau, Frédérique
Jouvenot, Damien
Lognon, Elise
Boggio-Pasqua, Martial
Royal, Guy
All Visible Light Photoswitch Based on the Dimethyldihydropyrene Unit Operating in Aqueous Solutions with High Quantum Yields
title All Visible Light Photoswitch Based on the Dimethyldihydropyrene Unit Operating in Aqueous Solutions with High Quantum Yields
title_full All Visible Light Photoswitch Based on the Dimethyldihydropyrene Unit Operating in Aqueous Solutions with High Quantum Yields
title_fullStr All Visible Light Photoswitch Based on the Dimethyldihydropyrene Unit Operating in Aqueous Solutions with High Quantum Yields
title_full_unstemmed All Visible Light Photoswitch Based on the Dimethyldihydropyrene Unit Operating in Aqueous Solutions with High Quantum Yields
title_short All Visible Light Photoswitch Based on the Dimethyldihydropyrene Unit Operating in Aqueous Solutions with High Quantum Yields
title_sort all visible light photoswitch based on the dimethyldihydropyrene unit operating in aqueous solutions with high quantum yields
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9875246/
https://www.ncbi.nlm.nih.gov/pubmed/36711101
http://dx.doi.org/10.1021/jacsau.2c00552
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