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Going beyond the borders: pyrrolo[3,2-b]pyrroles with deep red emission
A two-step route to strongly absorbing and efficiently orange to deep red fluorescent, doubly B/N-doped, ladder-type pyrrolo[3,2-b]pyrroles has been developed. We synthesize and study a series of derivatives of these four-coordinate boron-containing, nominally quadrupolar materials, which mostly exh...
Autores principales: | , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8672719/ https://www.ncbi.nlm.nih.gov/pubmed/35024117 http://dx.doi.org/10.1039/d1sc05007a |
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author | Tasior, Mariusz Kowalczyk, Paweł Przybył, Marta Czichy, Małgorzata Janasik, Patryk Bousquet, Manon H. E. Łapkowski, Mieczysław Rammo, Matt Rebane, Aleksander Jacquemin, Denis Gryko, Daniel T. |
author_facet | Tasior, Mariusz Kowalczyk, Paweł Przybył, Marta Czichy, Małgorzata Janasik, Patryk Bousquet, Manon H. E. Łapkowski, Mieczysław Rammo, Matt Rebane, Aleksander Jacquemin, Denis Gryko, Daniel T. |
author_sort | Tasior, Mariusz |
collection | PubMed |
description | A two-step route to strongly absorbing and efficiently orange to deep red fluorescent, doubly B/N-doped, ladder-type pyrrolo[3,2-b]pyrroles has been developed. We synthesize and study a series of derivatives of these four-coordinate boron-containing, nominally quadrupolar materials, which mostly exhibit one-photon absorption in the 500–600 nm range with the peak molar extinction coefficients reaching 150 000, and emission in the 520–670 nm range with the fluorescence quantum yields reaching 0.90. Within the family of these ultrastable dyes even small structural changes lead to significant variations of the photophysical properties, in some cases attributed to reversal of energy ordering of alternate-parity excited electronic states. Effective preservation of ground-state inversion symmetry was evidenced by very weak two-photon absorption (2PA) at excitation wavelengths corresponding to the lowest-energy, strongly one-photon allowed purely electronic transition. π-Expanded derivatives and those possessing electron-donating groups showed the most red-shifted absorption- and emission spectra, while displaying remarkably high peak 2PA cross-section (σ(2PA)) values reaching ∼2400 GM at around 760 nm, corresponding to a two-photon allowed higher-energy excited state. At the same time, derivatives lacking π-expansion were found to have a relatively weak 2PA peak centered at ca. 800–900 nm with the maximum σ(2PA) ∼50–250 GM. Our findings are augmented by theoretical calculations performed using TD-DFT method, which reproduce the main experimental trends, including the 2PA, in a nearly quantitative manner. Electrochemical studies revealed that the HOMO of the new dyes is located at ca. −5.35 eV making them relatively electron rich in spite of the presence of two B(−)–N(+) dative bonds. These dyes undergo a fully reversible first oxidation, located on the diphenylpyrrolo[3,2-b]pyrrole core, directly to the di(radical cation) stage. |
format | Online Article Text |
id | pubmed-8672719 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-86727192022-01-11 Going beyond the borders: pyrrolo[3,2-b]pyrroles with deep red emission Tasior, Mariusz Kowalczyk, Paweł Przybył, Marta Czichy, Małgorzata Janasik, Patryk Bousquet, Manon H. E. Łapkowski, Mieczysław Rammo, Matt Rebane, Aleksander Jacquemin, Denis Gryko, Daniel T. Chem Sci Chemistry A two-step route to strongly absorbing and efficiently orange to deep red fluorescent, doubly B/N-doped, ladder-type pyrrolo[3,2-b]pyrroles has been developed. We synthesize and study a series of derivatives of these four-coordinate boron-containing, nominally quadrupolar materials, which mostly exhibit one-photon absorption in the 500–600 nm range with the peak molar extinction coefficients reaching 150 000, and emission in the 520–670 nm range with the fluorescence quantum yields reaching 0.90. Within the family of these ultrastable dyes even small structural changes lead to significant variations of the photophysical properties, in some cases attributed to reversal of energy ordering of alternate-parity excited electronic states. Effective preservation of ground-state inversion symmetry was evidenced by very weak two-photon absorption (2PA) at excitation wavelengths corresponding to the lowest-energy, strongly one-photon allowed purely electronic transition. π-Expanded derivatives and those possessing electron-donating groups showed the most red-shifted absorption- and emission spectra, while displaying remarkably high peak 2PA cross-section (σ(2PA)) values reaching ∼2400 GM at around 760 nm, corresponding to a two-photon allowed higher-energy excited state. At the same time, derivatives lacking π-expansion were found to have a relatively weak 2PA peak centered at ca. 800–900 nm with the maximum σ(2PA) ∼50–250 GM. Our findings are augmented by theoretical calculations performed using TD-DFT method, which reproduce the main experimental trends, including the 2PA, in a nearly quantitative manner. Electrochemical studies revealed that the HOMO of the new dyes is located at ca. −5.35 eV making them relatively electron rich in spite of the presence of two B(−)–N(+) dative bonds. These dyes undergo a fully reversible first oxidation, located on the diphenylpyrrolo[3,2-b]pyrrole core, directly to the di(radical cation) stage. The Royal Society of Chemistry 2021-11-22 /pmc/articles/PMC8672719/ /pubmed/35024117 http://dx.doi.org/10.1039/d1sc05007a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Tasior, Mariusz Kowalczyk, Paweł Przybył, Marta Czichy, Małgorzata Janasik, Patryk Bousquet, Manon H. E. Łapkowski, Mieczysław Rammo, Matt Rebane, Aleksander Jacquemin, Denis Gryko, Daniel T. Going beyond the borders: pyrrolo[3,2-b]pyrroles with deep red emission |
title | Going beyond the borders: pyrrolo[3,2-b]pyrroles with deep red emission |
title_full | Going beyond the borders: pyrrolo[3,2-b]pyrroles with deep red emission |
title_fullStr | Going beyond the borders: pyrrolo[3,2-b]pyrroles with deep red emission |
title_full_unstemmed | Going beyond the borders: pyrrolo[3,2-b]pyrroles with deep red emission |
title_short | Going beyond the borders: pyrrolo[3,2-b]pyrroles with deep red emission |
title_sort | going beyond the borders: pyrrolo[3,2-b]pyrroles with deep red emission |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8672719/ https://www.ncbi.nlm.nih.gov/pubmed/35024117 http://dx.doi.org/10.1039/d1sc05007a |
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