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Diphenylanthracene Dimers for Triplet–Triplet Annihilation Photon Upconversion: Mechanistic Insights for Intramolecular Pathways and the Importance of Molecular Geometry

[Image: see text] Novel approaches to modify the spectral output of the sun have seen a surge in interest recently, with triplet–triplet annihilation driven photon upconversion (TTA-UC) gaining widespread recognition due to its ability to function under low-intensity, noncoherent light. Herein, four...

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Autores principales: Olesund, Axel, Gray, Victor, Mårtensson, Jerker, Albinsson, Bo
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8154513/
https://www.ncbi.nlm.nih.gov/pubmed/33835789
http://dx.doi.org/10.1021/jacs.1c00331
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author Olesund, Axel
Gray, Victor
Mårtensson, Jerker
Albinsson, Bo
author_facet Olesund, Axel
Gray, Victor
Mårtensson, Jerker
Albinsson, Bo
author_sort Olesund, Axel
collection PubMed
description [Image: see text] Novel approaches to modify the spectral output of the sun have seen a surge in interest recently, with triplet–triplet annihilation driven photon upconversion (TTA-UC) gaining widespread recognition due to its ability to function under low-intensity, noncoherent light. Herein, four diphenylanthracene (DPA) dimers are investigated to explore how the structure of these dimers affects upconversion efficiency. Also, the mechanism responsible for intramolecular upconversion is elucidated. In particular, two models are compared using steady-state and time-resolved simulations of the TTA-UC emission intensities and kinetics. All dimers perform TTA-UC efficiently in the presence of the sensitizer platinum octaethylporphyrin. The meta-coupled dimer 1,3-DPA(2) performs best yielding a 21.2% upconversion quantum yield (out of a 50% maximum), which is close to that of the reference monomer DPA (24.0%). Its superior performance compared to the other dimers is primarily ascribed to the longer triplet lifetime of this dimer (4.7 ms), thus reinforcing the importance of this parameter. Comparisons between simulations and experiments reveal that the double-sensitization mechanism is part of the mechanism of intramolecular upconversion and that this additional pathway could be of great significance under specific conditions. The results from this study can thus act as a guide not only in terms of annihilator design but also for the design of future solid-state systems where intramolecular exciton migration is anticipated to play a major role.
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spelling pubmed-81545132021-05-27 Diphenylanthracene Dimers for Triplet–Triplet Annihilation Photon Upconversion: Mechanistic Insights for Intramolecular Pathways and the Importance of Molecular Geometry Olesund, Axel Gray, Victor Mårtensson, Jerker Albinsson, Bo J Am Chem Soc [Image: see text] Novel approaches to modify the spectral output of the sun have seen a surge in interest recently, with triplet–triplet annihilation driven photon upconversion (TTA-UC) gaining widespread recognition due to its ability to function under low-intensity, noncoherent light. Herein, four diphenylanthracene (DPA) dimers are investigated to explore how the structure of these dimers affects upconversion efficiency. Also, the mechanism responsible for intramolecular upconversion is elucidated. In particular, two models are compared using steady-state and time-resolved simulations of the TTA-UC emission intensities and kinetics. All dimers perform TTA-UC efficiently in the presence of the sensitizer platinum octaethylporphyrin. The meta-coupled dimer 1,3-DPA(2) performs best yielding a 21.2% upconversion quantum yield (out of a 50% maximum), which is close to that of the reference monomer DPA (24.0%). Its superior performance compared to the other dimers is primarily ascribed to the longer triplet lifetime of this dimer (4.7 ms), thus reinforcing the importance of this parameter. Comparisons between simulations and experiments reveal that the double-sensitization mechanism is part of the mechanism of intramolecular upconversion and that this additional pathway could be of great significance under specific conditions. The results from this study can thus act as a guide not only in terms of annihilator design but also for the design of future solid-state systems where intramolecular exciton migration is anticipated to play a major role. American Chemical Society 2021-04-09 2021-04-21 /pmc/articles/PMC8154513/ /pubmed/33835789 http://dx.doi.org/10.1021/jacs.1c00331 Text en © 2021 The Authors. Published by American Chemical Society 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 Olesund, Axel
Gray, Victor
Mårtensson, Jerker
Albinsson, Bo
Diphenylanthracene Dimers for Triplet–Triplet Annihilation Photon Upconversion: Mechanistic Insights for Intramolecular Pathways and the Importance of Molecular Geometry
title Diphenylanthracene Dimers for Triplet–Triplet Annihilation Photon Upconversion: Mechanistic Insights for Intramolecular Pathways and the Importance of Molecular Geometry
title_full Diphenylanthracene Dimers for Triplet–Triplet Annihilation Photon Upconversion: Mechanistic Insights for Intramolecular Pathways and the Importance of Molecular Geometry
title_fullStr Diphenylanthracene Dimers for Triplet–Triplet Annihilation Photon Upconversion: Mechanistic Insights for Intramolecular Pathways and the Importance of Molecular Geometry
title_full_unstemmed Diphenylanthracene Dimers for Triplet–Triplet Annihilation Photon Upconversion: Mechanistic Insights for Intramolecular Pathways and the Importance of Molecular Geometry
title_short Diphenylanthracene Dimers for Triplet–Triplet Annihilation Photon Upconversion: Mechanistic Insights for Intramolecular Pathways and the Importance of Molecular Geometry
title_sort diphenylanthracene dimers for triplet–triplet annihilation photon upconversion: mechanistic insights for intramolecular pathways and the importance of molecular geometry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8154513/
https://www.ncbi.nlm.nih.gov/pubmed/33835789
http://dx.doi.org/10.1021/jacs.1c00331
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