Luminescent Trityl-based Diradicaloids: A Theoretical and Experimental Assessment of Charge-Resonance in Low-Lying Excited States
The tris(2,4,6-trichlorophenyl)methyl radical (TTM) has inspired the synthesis of several luminescent diradicaloids, providing an extraordinary opportunity to control the nature of the low-lying excited states by fine-tuning the diradical character. However, the photophysical properties of TTM-deriv...
| Autores: | , , , , , , , , , , |
|---|---|
| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2025 |
| País: | España |
| Institución: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositorio: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/393992 |
| Acceso en línea: | http://hdl.handle.net/10261/393992 https://api.elsevier.com/content/abstract/scopus_id/105003136241 |
| Access Level: | acceso abierto |
| Palabra clave: | Chichibabin hydrocarbon Charge resonance Doubly excited state Luminescent organic diradicals Polyhalogenated trityl radicals |
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Luminescent Trityl-based Diradicaloids: A Theoretical and Experimental Assessment of Charge-Resonance in Low-Lying Excited States |
| title |
Luminescent Trityl-based Diradicaloids: A Theoretical and Experimental Assessment of Charge-Resonance in Low-Lying Excited States |
| spellingShingle |
Luminescent Trityl-based Diradicaloids: A Theoretical and Experimental Assessment of Charge-Resonance in Low-Lying Excited States Mesto, Davide Chichibabin hydrocarbon Charge resonance Doubly excited state Luminescent organic diradicals Polyhalogenated trityl radicals |
| title_short |
Luminescent Trityl-based Diradicaloids: A Theoretical and Experimental Assessment of Charge-Resonance in Low-Lying Excited States |
| title_full |
Luminescent Trityl-based Diradicaloids: A Theoretical and Experimental Assessment of Charge-Resonance in Low-Lying Excited States |
| title_fullStr |
Luminescent Trityl-based Diradicaloids: A Theoretical and Experimental Assessment of Charge-Resonance in Low-Lying Excited States |
| title_full_unstemmed |
Luminescent Trityl-based Diradicaloids: A Theoretical and Experimental Assessment of Charge-Resonance in Low-Lying Excited States |
| title_sort |
Luminescent Trityl-based Diradicaloids: A Theoretical and Experimental Assessment of Charge-Resonance in Low-Lying Excited States |
| dc.creator.none.fl_str_mv |
Mesto, Davide Orza, Michele Bardi, Brunella Punzi, Angela Ratera, Immaculada Veciana, Jaume Farinola, Gianluca Painelli, Anna Terenziani, Francesca Blasi, Davide Negri, Fabrizia |
| author |
Mesto, Davide |
| author_facet |
Mesto, Davide Orza, Michele Bardi, Brunella Punzi, Angela Ratera, Immaculada Veciana, Jaume Farinola, Gianluca Painelli, Anna Terenziani, Francesca Blasi, Davide Negri, Fabrizia |
| author_role |
author |
| author2 |
Orza, Michele Bardi, Brunella Punzi, Angela Ratera, Immaculada Veciana, Jaume Farinola, Gianluca Painelli, Anna Terenziani, Francesca Blasi, Davide Negri, Fabrizia |
| author2_role |
author author author author author author author author author author |
| dc.contributor.none.fl_str_mv |
European Commission Ministero dell'Università e della Ricerca Ministerio de Ciencia e Innovación (España) Agencia Estatal de Investigación (España) Generalitat de Catalunya Instituto de Salud Carlos III Centro de Investigación Biomédica en Red Bioingeniería, Biomateriales y Nanomedicina (España) Università di Bologna Mesto, Davide [0009-0007-4134-3842] Orza, Michele [0000-0002-4935-6986] Bardi, Brunella [0000-0003-2686-1119] Punzi, Angela [0000-0001-5948-6373] Ratera, Immaculada [0000-0002-1464-9789] Veciana, Jaume [0000-0003-1023-9923] Farinola, Gianluca [0000-0002-1601-2810] Painelli, Anna [0000-0002-3500-3848] Terenziani, Francesca [0000-0001-5162-9210] Blasi, Davide [0000-0002-6887-3364] Negri, Fabrizia [0000-0002-0359-0128] Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72] |
| dc.subject.none.fl_str_mv |
Chichibabin hydrocarbon Charge resonance Doubly excited state Luminescent organic diradicals Polyhalogenated trityl radicals |
| topic |
Chichibabin hydrocarbon Charge resonance Doubly excited state Luminescent organic diradicals Polyhalogenated trityl radicals |
| description |
The tris(2,4,6-trichlorophenyl)methyl radical (TTM) has inspired the synthesis of several luminescent diradicaloids, providing an extraordinary opportunity to control the nature of the low-lying excited states by fine-tuning the diradical character. However, the photophysical properties of TTM-derived diradicals remain not fully understood yet. Here we present a combined theoretical and experimental investigation to elucidate the origin of their luminescence. The theoretical analysis explores a series of symmetric TTM-derived diradicals with singlet ground state and increasingly longer π-conjugated spacers between radical moieties, focussing on the nature of the lowest excited electronic states governing their photophysics. The study is complemented by a complete spectroscopic characterization of the TTM-TTM diradical, synthesized using a novel, simpler and more efficient procedure exploiting the unique reactivity of TTM. The diradicals feature two novel low-lying excited states, absent in TTM, arising from charge resonance (CR) between the radical units. The lowest CR state is characterized by the H,H→L,L double excitation (DE) and is a dark state for symmetric diradicals. The CR nature explains the blue-shifted emission observed by increasing the distance between the radical centres as seen in TTM-ph-TTM. This insight suggests different design strategies to improve the luminescence properties of TTM-derived diradicals. |
| publishDate |
2025 |
| dc.date.none.fl_str_mv |
2025 2025 2025 |
| dc.type.none.fl_str_mv |
info:eu-repo/semantics/article http://purl.org/coar/resource_type/c_6501 Publisher's version info:eu-repo/semantics/publishedVersion |
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article |
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publishedVersion |
| dc.identifier.none.fl_str_mv |
http://hdl.handle.net/10261/393992 https://api.elsevier.com/content/abstract/scopus_id/105003136241 |
| url |
http://hdl.handle.net/10261/393992 https://api.elsevier.com/content/abstract/scopus_id/105003136241 |
| dc.language.none.fl_str_mv |
Inglés |
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Inglés |
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#PLACEHOLDER_PARENT_METADATA_VALUE# #PLACEHOLDER_PARENT_METADATA_VALUE# info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-137332OB-I00 info:eu-repo/grantAgreement/AEI/Plan Estatal de investigación Científica y Técnica y de Innovación 2021-2023/CEX2023-001263-S Chemistry (Weinheim an der Bergstrasse, Germany) http://doi.org/10.1002/chem.202500749 Sí |
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info:eu-repo/semantics/openAccess |
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openAccess |
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Wiley-VCH |
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Wiley-VCH |
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reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC instname:Consejo Superior de Investigaciones Científicas (CSIC) |
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DIGITAL.CSIC. Repositorio Institucional del CSIC |
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DIGITAL.CSIC. Repositorio Institucional del CSIC |
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Luminescent Trityl-based Diradicaloids: A Theoretical and Experimental Assessment of Charge-Resonance in Low-Lying Excited StatesMesto, DavideOrza, MicheleBardi, BrunellaPunzi, AngelaRatera, ImmaculadaVeciana, JaumeFarinola, GianlucaPainelli, AnnaTerenziani, FrancescaBlasi, DavideNegri, FabriziaChichibabin hydrocarbonCharge resonanceDoubly excited stateLuminescent organic diradicalsPolyhalogenated trityl radicalsThe tris(2,4,6-trichlorophenyl)methyl radical (TTM) has inspired the synthesis of several luminescent diradicaloids, providing an extraordinary opportunity to control the nature of the low-lying excited states by fine-tuning the diradical character. However, the photophysical properties of TTM-derived diradicals remain not fully understood yet. Here we present a combined theoretical and experimental investigation to elucidate the origin of their luminescence. The theoretical analysis explores a series of symmetric TTM-derived diradicals with singlet ground state and increasingly longer π-conjugated spacers between radical moieties, focussing on the nature of the lowest excited electronic states governing their photophysics. The study is complemented by a complete spectroscopic characterization of the TTM-TTM diradical, synthesized using a novel, simpler and more efficient procedure exploiting the unique reactivity of TTM. The diradicals feature two novel low-lying excited states, absent in TTM, arising from charge resonance (CR) between the radical units. The lowest CR state is characterized by the H,H→L,L double excitation (DE) and is a dark state for symmetric diradicals. The CR nature explains the blue-shifted emission observed by increasing the distance between the radical centres as seen in TTM-ph-TTM. This insight suggests different design strategies to improve the luminescence properties of TTM-derived diradicals.D.M. gratefully acknowledges the PON-RI Industrial Chemical and Molecular Sciences PhD XXXVII cycle action for funding, an initiative co-founded by European Union through the PON2022-2025 for Green and Innovation topics (ID grant 634338). M.O., D.B., A.Pu. and F.N. acknowledge funding from Ministero dell'Università e della Ricerca (MUR) PRIN 2022 project 202253P3YJ MULTIRADICALS4LIGHT: Design, synthesis, and characterization of inert MULTIfunctional diRADICALoidS for organic LIGHT-emitting transistors. A.Pa. and G.F. acknowledge PNRR MUR project PE0000023-NQSTI. B.B., A.Pa. and F.T. acknowledge the equipment and framework of the COMP−R Initiatives, funded by the “Departments of Excellence program of the Italian Ministry for University and Research” (MUR, 2023–2027). Financial support by the MICIU of Spain (projects PID2022-137332OBI00, CEX2023- 001263-S) and the Generalitat de Catalunya (project SGR Cat 2021-00438), Instituto de Salud Carlos III and the Networking Research Center on Bioengineering, Biomaterials, and Nanomedicine (CIBERBBN), COST Action LUCES CA22131. This research work has also been funded by the European Commission – NextGenerationEU (Regulation EU 2020/2094), through CSIC′s Quantum Technologies Platform (QTEP) and by the Quantera project OPTRIBITS PCI2024-153480. Open Access publishing facilitated by Università degli Studi di Bologna, as part of the Wiley - CRUI-CARE agreement.With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2023-001263-S).Peer reviewedWiley-VCHEuropean CommissionMinistero dell'Università e della RicercaMinisterio de Ciencia e Innovación (España)Agencia Estatal de Investigación (España)Generalitat de CatalunyaInstituto de Salud Carlos IIICentro de Investigación Biomédica en Red Bioingeniería, Biomateriales y Nanomedicina (España)Università di BolognaMesto, Davide [0009-0007-4134-3842]Orza, Michele [0000-0002-4935-6986]Bardi, Brunella [0000-0003-2686-1119]Punzi, Angela [0000-0001-5948-6373]Ratera, Immaculada [0000-0002-1464-9789]Veciana, Jaume [0000-0003-1023-9923]Farinola, Gianluca [0000-0002-1601-2810]Painelli, Anna [0000-0002-3500-3848]Terenziani, Francesca [0000-0001-5162-9210]Blasi, Davide [0000-0002-6887-3364]Negri, Fabrizia [0000-0002-0359-0128]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202520252025info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/393992https://api.elsevier.com/content/abstract/scopus_id/105003136241reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-137332OB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de investigación Científica y Técnica y de Innovación 2021-2023/CEX2023-001263-SChemistry (Weinheim an der Bergstrasse, Germany)http://doi.org/10.1002/chem.202500749Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3939922026-05-22T06:33:51Z |
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15,81155 |