Intramolecular Triplet Diffusion Facilitates Triplet Dissociation in a Pentacene Hexamer
Triplet dynamics in singlet fission depend strongly on the strength of the electronic coupling. Covalent systems in solution offer precise control over such couplings. Nonetheless, efficient free triplet generation remains elusive in most systems, as the intermediate triplet pair ¹(T₁T₁) is prone to...
| Autores: | , , , , , , , , , , , |
|---|---|
| Formato: | artículo |
| Fecha de publicación: | 2024 |
| País: | España |
| Recursos: | Universidad Autónoma de Madrid |
| Repositorio: | Biblos-e Archivo. Repositorio Institucional de la UAM |
| Idioma: | inglés |
| OAI Identifier: | oai:repositorio.uam.es:10486/715758 |
| Acesso em linha: | http://hdl.handle.net/10486/715758 https://dx.doi.org/10.1002/anie.202315064 |
| Access Level: | acceso abierto |
| Palavra-chave: | Oligoacene photoenergy conversion singlet fission triplet dissociation ultrafast spectroscopy Química |
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Intramolecular Triplet Diffusion Facilitates Triplet Dissociation in a Pentacene HexamerGreiße, Phillip M.Thiel, DominikGotfredsen, HenrikChen, LanKrug, MarcelPapadopoulos, IliasMiskolzie, MarkClark, TimothyBrøndsted Nielsen, MogensTykwinski, Rik R.Guldi, Dirk M.Torres Cebada, TomásOligoacenephotoenergy conversionsinglet fissiontriplet dissociationultrafast spectroscopyQuímicaTriplet dynamics in singlet fission depend strongly on the strength of the electronic coupling. Covalent systems in solution offer precise control over such couplings. Nonetheless, efficient free triplet generation remains elusive in most systems, as the intermediate triplet pair ¹(T₁T₁) is prone to triplet-triplet annihilation due to its spatial confinement. In the solid state, entropically driven triplet diffusion assists in the spatial separation of triplets, resulting in higher yields of free triplets. Control over electronic coupling in the solid state is, however, challenging given its sensitivity to molecular packing. We have thus developed a hexameric system (HexPnc) to enable solid-state-like triplet diffusion at the molecular scale. This system is realized by covalently tethering three pentacene dimers to a central subphthalocyanine scaffold. Transient absorption spectroscopy, complemented by theoretical structural optimizations and steady-state spectroscopy, reveals that triplet diffusion is indeed facilitated due to intramolecular cluster formation. The yield of free triplets in HexPnc is increased by a factor of up to 14 compared to the corresponding dimeric reference (DiPnc). Thus, HexPnc establishes crucial design aspects for achieving efficient triplet dissociation in strongly coupled systems by providing avenues for diffusive separation of ¹(T₁T₁), while, concomitantly, retaining strong interchromophore coupling which preserves rapid formation of ¹(T₁T₁)R.R.T. acknowledges funding from the Natural Sciences and Engineering Research Council of Canada (NSERC, grant no. RGPIN-2017-05052) and the Canada Foundation for Innovation (CFI). D.M.G. acknowledges financial support from the Deutsche Forschungsgemeinschaft (DFG) as part of SFB 953 “Synthetic Carbon Allotropes” and GU 517/32- 1. T.T. acknowledges financial support from the Spanish MCIN/AEI/10.13039/501100011033 (PID2020- 116490GB I00, TED2021-131255B C43), the Comunidad de Madrid and the Spanish State through the Recovery, Transformation and Resilience Plan [“Materiales Disruptivos Bidimensionales (2D)” (MAD2D-CM) (UAM1)-MRR Materiales Avanzados], and the European Union through the Next Generation EU funds. IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV2016-0686). T. T. also acknowledges the Alexander von Humboldt Foundation (Germany) for the A. v. Humboldt— J. C. Mutis Research Award 2023 (Ref [3].3-1231125—ESPGSA). H.G. thanks the Danish Ministry of Higher Education and Science for an EliteForsk travel scholarship (6161- 00051B). Open Access funding enabled and organized by Projekt DEALWiley-BlackwellDepartamento de Química OrgánicaFacultad de Ciencias20242024-01-24research articlehttp://purl.org/coar/resource_type/c_2df8fbb1VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/715758https://dx.doi.org/10.1002/anie.202315064reponame:Biblos-e Archivo. Repositorio Institucional de la UAMinstname:Universidad Autónoma de MadridInglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:repositorio.uam.es:10486/7157582026-06-23T12:46:27Z |
| dc.title.none.fl_str_mv |
Intramolecular Triplet Diffusion Facilitates Triplet Dissociation in a Pentacene Hexamer |
| title |
Intramolecular Triplet Diffusion Facilitates Triplet Dissociation in a Pentacene Hexamer |
| spellingShingle |
Intramolecular Triplet Diffusion Facilitates Triplet Dissociation in a Pentacene Hexamer Greiße, Phillip M. Oligoacene photoenergy conversion singlet fission triplet dissociation ultrafast spectroscopy Química |
| title_short |
Intramolecular Triplet Diffusion Facilitates Triplet Dissociation in a Pentacene Hexamer |
| title_full |
Intramolecular Triplet Diffusion Facilitates Triplet Dissociation in a Pentacene Hexamer |
| title_fullStr |
Intramolecular Triplet Diffusion Facilitates Triplet Dissociation in a Pentacene Hexamer |
| title_full_unstemmed |
Intramolecular Triplet Diffusion Facilitates Triplet Dissociation in a Pentacene Hexamer |
| title_sort |
Intramolecular Triplet Diffusion Facilitates Triplet Dissociation in a Pentacene Hexamer |
| dc.creator.none.fl_str_mv |
Greiße, Phillip M. Thiel, Dominik Gotfredsen, Henrik Chen, Lan Krug, Marcel Papadopoulos, Ilias Miskolzie, Mark Clark, Timothy Brøndsted Nielsen, Mogens Tykwinski, Rik R. Guldi, Dirk M. Torres Cebada, Tomás |
| author |
Greiße, Phillip M. |
| author_facet |
Greiße, Phillip M. Thiel, Dominik Gotfredsen, Henrik Chen, Lan Krug, Marcel Papadopoulos, Ilias Miskolzie, Mark Clark, Timothy Brøndsted Nielsen, Mogens Tykwinski, Rik R. Guldi, Dirk M. Torres Cebada, Tomás |
| author_role |
author |
| author2 |
Thiel, Dominik Gotfredsen, Henrik Chen, Lan Krug, Marcel Papadopoulos, Ilias Miskolzie, Mark Clark, Timothy Brøndsted Nielsen, Mogens Tykwinski, Rik R. Guldi, Dirk M. Torres Cebada, Tomás |
| author2_role |
author author author author author author author author author author author |
| dc.contributor.none.fl_str_mv |
Departamento de Química Orgánica Facultad de Ciencias |
| dc.subject.none.fl_str_mv |
Oligoacene photoenergy conversion singlet fission triplet dissociation ultrafast spectroscopy Química |
| topic |
Oligoacene photoenergy conversion singlet fission triplet dissociation ultrafast spectroscopy Química |
| description |
Triplet dynamics in singlet fission depend strongly on the strength of the electronic coupling. Covalent systems in solution offer precise control over such couplings. Nonetheless, efficient free triplet generation remains elusive in most systems, as the intermediate triplet pair ¹(T₁T₁) is prone to triplet-triplet annihilation due to its spatial confinement. In the solid state, entropically driven triplet diffusion assists in the spatial separation of triplets, resulting in higher yields of free triplets. Control over electronic coupling in the solid state is, however, challenging given its sensitivity to molecular packing. We have thus developed a hexameric system (HexPnc) to enable solid-state-like triplet diffusion at the molecular scale. This system is realized by covalently tethering three pentacene dimers to a central subphthalocyanine scaffold. Transient absorption spectroscopy, complemented by theoretical structural optimizations and steady-state spectroscopy, reveals that triplet diffusion is indeed facilitated due to intramolecular cluster formation. The yield of free triplets in HexPnc is increased by a factor of up to 14 compared to the corresponding dimeric reference (DiPnc). Thus, HexPnc establishes crucial design aspects for achieving efficient triplet dissociation in strongly coupled systems by providing avenues for diffusive separation of ¹(T₁T₁), while, concomitantly, retaining strong interchromophore coupling which preserves rapid formation of ¹(T₁T₁) |
| publishDate |
2024 |
| dc.date.none.fl_str_mv |
2024 2024-01-24 |
| dc.type.none.fl_str_mv |
research article http://purl.org/coar/resource_type/c_2df8fbb1 VoR http://purl.org/coar/version/c_970fb48d4fbd8a85 |
| dc.type.openaire.fl_str_mv |
info:eu-repo/semantics/article |
| format |
article |
| dc.identifier.none.fl_str_mv |
http://hdl.handle.net/10486/715758 https://dx.doi.org/10.1002/anie.202315064 |
| url |
http://hdl.handle.net/10486/715758 https://dx.doi.org/10.1002/anie.202315064 |
| dc.language.none.fl_str_mv |
Inglés eng |
| language_invalid_str_mv |
Inglés |
| language |
eng |
| dc.rights.none.fl_str_mv |
open access http://purl.org/coar/access_right/c_abf2 Attribution 4.0 International http://creativecommons.org/licenses/by/4.0/ |
| dc.rights.openaire.fl_str_mv |
info:eu-repo/semantics/openAccess |
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open access http://purl.org/coar/access_right/c_abf2 Attribution 4.0 International http://creativecommons.org/licenses/by/4.0/ |
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openAccess |
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application/pdf |
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Wiley-Blackwell |
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Wiley-Blackwell |
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reponame:Biblos-e Archivo. Repositorio Institucional de la UAM instname:Universidad Autónoma de Madrid |
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Universidad Autónoma de Madrid |
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Biblos-e Archivo. Repositorio Institucional de la UAM |
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Biblos-e Archivo. Repositorio Institucional de la UAM |
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