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Long-lived triplet charge-separated state in naphthalenediimide based donor–acceptor systems

1,4,5,8-Naphthalenediimides (NDIs) are widely used motifs to design multichromophoric architectures due to their ease of functionalisation, their high oxidative power and the stability of their radical anion. The NDI building block can be incorporated in supramolecular systems by either core or imid...

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Autores principales: Aster, Alexander, Rumble, Christopher, Bornhof, Anna-Bea, Huang, Hsin-Hua, Sakai, Naomi, Šolomek, Tomáš, Matile, Stefan, Vauthey, Eric
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8179635/
https://www.ncbi.nlm.nih.gov/pubmed/34168763
http://dx.doi.org/10.1039/d1sc00285f
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author Aster, Alexander
Rumble, Christopher
Bornhof, Anna-Bea
Huang, Hsin-Hua
Sakai, Naomi
Šolomek, Tomáš
Matile, Stefan
Vauthey, Eric
author_facet Aster, Alexander
Rumble, Christopher
Bornhof, Anna-Bea
Huang, Hsin-Hua
Sakai, Naomi
Šolomek, Tomáš
Matile, Stefan
Vauthey, Eric
author_sort Aster, Alexander
collection PubMed
description 1,4,5,8-Naphthalenediimides (NDIs) are widely used motifs to design multichromophoric architectures due to their ease of functionalisation, their high oxidative power and the stability of their radical anion. The NDI building block can be incorporated in supramolecular systems by either core or imide functionalization. We report on the charge-transfer dynamics of a series of electron donor–acceptor dyads consisting of a NDI chromophore with one or two donors linked at the axial, imide position. Photo-population of the core-centred π–π* state is followed by ultrafast electron transfer from the electron donor to the NDI. Due to a solvent dependent singlet–triplet equilibrium inherent to the NDI core, both singlet and triplet charge-separated states are populated. We demonstrate that long-lived charge separation in the triplet state can be achieved by controlling the mutual orientation of the donor–acceptor sub-units. By extending this study to a supramolecular NDI-based cage, we also show that the triplet charge-separation yield can be increased by tuning the environment.
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spelling pubmed-81796352021-06-23 Long-lived triplet charge-separated state in naphthalenediimide based donor–acceptor systems Aster, Alexander Rumble, Christopher Bornhof, Anna-Bea Huang, Hsin-Hua Sakai, Naomi Šolomek, Tomáš Matile, Stefan Vauthey, Eric Chem Sci Chemistry 1,4,5,8-Naphthalenediimides (NDIs) are widely used motifs to design multichromophoric architectures due to their ease of functionalisation, their high oxidative power and the stability of their radical anion. The NDI building block can be incorporated in supramolecular systems by either core or imide functionalization. We report on the charge-transfer dynamics of a series of electron donor–acceptor dyads consisting of a NDI chromophore with one or two donors linked at the axial, imide position. Photo-population of the core-centred π–π* state is followed by ultrafast electron transfer from the electron donor to the NDI. Due to a solvent dependent singlet–triplet equilibrium inherent to the NDI core, both singlet and triplet charge-separated states are populated. We demonstrate that long-lived charge separation in the triplet state can be achieved by controlling the mutual orientation of the donor–acceptor sub-units. By extending this study to a supramolecular NDI-based cage, we also show that the triplet charge-separation yield can be increased by tuning the environment. The Royal Society of Chemistry 2021-02-26 /pmc/articles/PMC8179635/ /pubmed/34168763 http://dx.doi.org/10.1039/d1sc00285f Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/
spellingShingle Chemistry
Aster, Alexander
Rumble, Christopher
Bornhof, Anna-Bea
Huang, Hsin-Hua
Sakai, Naomi
Šolomek, Tomáš
Matile, Stefan
Vauthey, Eric
Long-lived triplet charge-separated state in naphthalenediimide based donor–acceptor systems
title Long-lived triplet charge-separated state in naphthalenediimide based donor–acceptor systems
title_full Long-lived triplet charge-separated state in naphthalenediimide based donor–acceptor systems
title_fullStr Long-lived triplet charge-separated state in naphthalenediimide based donor–acceptor systems
title_full_unstemmed Long-lived triplet charge-separated state in naphthalenediimide based donor–acceptor systems
title_short Long-lived triplet charge-separated state in naphthalenediimide based donor–acceptor systems
title_sort long-lived triplet charge-separated state in naphthalenediimide based donor–acceptor systems
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8179635/
https://www.ncbi.nlm.nih.gov/pubmed/34168763
http://dx.doi.org/10.1039/d1sc00285f
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