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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...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2020
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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. |
format | Online Article Text |
id | pubmed-7027818 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
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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