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Two π‐Electrons Make the Difference: From BODIPY to BODIIM Switchable Fluorescent Dyes

(aza‐)BODIPY dyes (boron dipyrromethene dyes) are well‐established fluorophores due to their large quantum yields, stability, and diversity, which led to promising applications including imaging techniques, sensors, organic (opto)electronic materials, or biomedical applications. Although the control...

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Autores principales: Dolati, Hadi, Haufe, Lisa C., Denker, Lars, Lorbach, Andreas, Grotjahn, Robin, Hörner, Gerald, Frank, René
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7027818/
https://www.ncbi.nlm.nih.gov/pubmed/31774591
http://dx.doi.org/10.1002/chem.201905344
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author Dolati, Hadi
Haufe, Lisa C.
Denker, Lars
Lorbach, Andreas
Grotjahn, Robin
Hörner, Gerald
Frank, René
author_facet Dolati, Hadi
Haufe, Lisa C.
Denker, Lars
Lorbach, Andreas
Grotjahn, Robin
Hörner, Gerald
Frank, René
author_sort Dolati, Hadi
collection PubMed
description (aza‐)BODIPY dyes (boron dipyrromethene dyes) are well‐established fluorophores due to their large quantum yields, stability, and diversity, which led to promising applications including imaging techniques, sensors, organic (opto)electronic materials, or biomedical applications. Although the control of the optical properties in (aza‐)BODIPY dyes by peripheral functional groups is well studied, we herein present a novel approach to modify the 12 π‐electron core of the dipyrromethene scaffold. The replacement of two carbon atoms in the β‐position of a BODIPY dye by two nitrogen atoms afforded a 14 π‐electron system, which was termed BODIIM (boron diimidazolylmethene) in systematic analogy to the BODIPY dyes. Remarkably, the BODIIM dye was obtained with a BH(2)‐rigidifying entity, which is currently elusive and highly sought after for the BODIPY dye class. DFT‐Calculations confirm the [12+2] π‐electron relationship between BODIPY and BODIIM and reveal a strong shape correlation between LUMO in the BODIPY and the HOMO of the BODIIM. The modification of the π‐system leads to a dramatic shift of the optical properties, of which the fluorescent emission is most noteworthy and occurs at much larger Stokes shift, that is, ≈500 cm(−1) in BODIPY versus >4170 cm(−1) in BODIIM system in all solvents investigated. Nucleophilic reactivity was found at the meso‐carbon atom in the formation of stable borane adducts with a significant shift of the fluorescent emission, and this behavior contrasts the reactivity of conventional BODIPY systems. In addition, the reverse decomplexation of the borane adducts was demonstrated in reactions with a representative N‐heterocyclic carbene to retain the strongly fluorescent BODIIM compound, which suggests applications as fully reversible fluorescent switch.
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spelling pubmed-70278182020-02-24 Two π‐Electrons Make the Difference: From BODIPY to BODIIM Switchable Fluorescent Dyes Dolati, Hadi Haufe, Lisa C. Denker, Lars Lorbach, Andreas Grotjahn, Robin Hörner, Gerald Frank, René Chemistry Full Papers (aza‐)BODIPY dyes (boron dipyrromethene dyes) are well‐established fluorophores due to their large quantum yields, stability, and diversity, which led to promising applications including imaging techniques, sensors, organic (opto)electronic materials, or biomedical applications. Although the control of the optical properties in (aza‐)BODIPY dyes by peripheral functional groups is well studied, we herein present a novel approach to modify the 12 π‐electron core of the dipyrromethene scaffold. The replacement of two carbon atoms in the β‐position of a BODIPY dye by two nitrogen atoms afforded a 14 π‐electron system, which was termed BODIIM (boron diimidazolylmethene) in systematic analogy to the BODIPY dyes. Remarkably, the BODIIM dye was obtained with a BH(2)‐rigidifying entity, which is currently elusive and highly sought after for the BODIPY dye class. DFT‐Calculations confirm the [12+2] π‐electron relationship between BODIPY and BODIIM and reveal a strong shape correlation between LUMO in the BODIPY and the HOMO of the BODIIM. The modification of the π‐system leads to a dramatic shift of the optical properties, of which the fluorescent emission is most noteworthy and occurs at much larger Stokes shift, that is, ≈500 cm(−1) in BODIPY versus >4170 cm(−1) in BODIIM system in all solvents investigated. Nucleophilic reactivity was found at the meso‐carbon atom in the formation of stable borane adducts with a significant shift of the fluorescent emission, and this behavior contrasts the reactivity of conventional BODIPY systems. In addition, the reverse decomplexation of the borane adducts was demonstrated in reactions with a representative N‐heterocyclic carbene to retain the strongly fluorescent BODIIM compound, which suggests applications as fully reversible fluorescent switch. John Wiley and Sons Inc. 2020-01-09 2020-01-27 /pmc/articles/PMC7027818/ /pubmed/31774591 http://dx.doi.org/10.1002/chem.201905344 Text en © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Full Papers
Dolati, Hadi
Haufe, Lisa C.
Denker, Lars
Lorbach, Andreas
Grotjahn, Robin
Hörner, Gerald
Frank, René
Two π‐Electrons Make the Difference: From BODIPY to BODIIM Switchable Fluorescent Dyes
title Two π‐Electrons Make the Difference: From BODIPY to BODIIM Switchable Fluorescent Dyes
title_full Two π‐Electrons Make the Difference: From BODIPY to BODIIM Switchable Fluorescent Dyes
title_fullStr Two π‐Electrons Make the Difference: From BODIPY to BODIIM Switchable Fluorescent Dyes
title_full_unstemmed Two π‐Electrons Make the Difference: From BODIPY to BODIIM Switchable Fluorescent Dyes
title_short Two π‐Electrons Make the Difference: From BODIPY to BODIIM Switchable Fluorescent Dyes
title_sort two π‐electrons make the difference: from bodipy to bodiim switchable fluorescent dyes
topic Full Papers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7027818/
https://www.ncbi.nlm.nih.gov/pubmed/31774591
http://dx.doi.org/10.1002/chem.201905344
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