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Disentangling Radiative and Non-Radiative Deactivation Pathways in Cu<SUP>I</SUP> -Based TADF Emitters
Indexado
WoS WOS:001442456300001
DOI 10.1002/ANIE.202501407
Año 2025
Tipo artículo de investigación

Citas Totales

Autores Afiliación Chile

Instituciones Chile

% Participación
Internacional

Autores
Afiliación Extranjera

Instituciones
Extranjeras


Abstract



The analysis of thermally activated delayed fluorescence emitters traditionally neglects the temperature dependence of the non-radiative singlet and triplet decay rates, which, for systems with quantum yields significantly departing from unity, unavoidably leads to inaccurate determination of the relevant photophysical parameters. Here we address this issue by performing a detailed photophysical study in three solid-state CuI complexes with the general formula [Cu(dmp)(PPh3)X] (X = Cl, Br, I). Decomposition of the measured temperature-dependent lifetimes tau(T) into their radiative and non-radiative contributions demonstrates a significant temperature dependence of the non-radiative rates, which leads to large deviations of the singlet-triplet gaps Delta EST from those determined in the traditional way. Our detailed analysis further confirms that non-radiative parameters follow the energy gap law and that zero field splitting effects, which are unrecognizable in the bare tau(T) data, are governed by the heavy atom effect. Our analysis is supported by measurements of the decay of the prompt fluorescence which is dominated by kISC in the studied compounds.

Métricas Externas



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Disciplinas de Investigación



WOS
Chemistry, Multidisciplinary
Scopus
Sin Disciplinas
SciELO
Sin Disciplinas

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Publicaciones WoS (Ediciones: ISSHP, ISTP, AHCI, SSCI, SCI), Scopus, SciELO Chile.

Colaboración Institucional



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Autores - Afiliación



Ord. Autor Género Institución - País
1 Llanos, Leonel - Universidad de Santiago de Chile - Chile
2 Staforelli, Sebastian - Universidad de Santiago de Chile - Chile
3 Oliver, Allen G. - UNIV NOTRE DAME - Estados Unidos
4 Moscoso, Francisco G. - Univ Pablo Olavide - España
5 Wannemacher, Reinhold - Ciudad Univ Cantoblanco - España
6 Cabanillas-Gonzalez, Juan Hombre Ciudad Univ Cantoblanco - España
7 Lemus, Luis - Universidad de Santiago de Chile - Chile
8 Aravena, Daniel - Universidad de Santiago de Chile - Chile

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Financiamiento



Fuente
Spanish Ministry of Science and Innovation
Fondecyt Regular
supercomputing infrastructure of the NLHPC
Fondecyt Regular Project
Regional Government of Madrid
Spanish Ministry for Science (MINECO/MICINN-FEDER)
The 'Severo Ochoa' Programme for Centres of Excellence in R&D of the Spanish Ministry of Science and Innovation

Muestra la fuente de financiamiento declarada en la publicación.

Agradecimientos



Agradecimiento
D.A. thanks FONDECYT Regular 1210325 for financial support. Powered@NLHPC: This research was partially supported by the Supercomputing Infrastructure of the NLHPC (CCSS210001). L. Lemus thanks Fondecyt Regular 1231787 project for financial support. J.C.G. and R.W. acknowledge support by the Spanish Ministry for Science (MINECO/MICINN-FEDER projects RTI2018-097508-B-I00, PID2021-128313OB-I00, TED2021-131018B-C22) and by the Regional Government of Madrid (NMAT2DCM). J.C.G. acknowledges a Research Consolidation Grant (CNS2022-136191) and project PDC202-314587-1I00, both from the Spanish Ministry of Science and Innovation. IMDEA Nanociencia acknowledges support from the 'Severo Ochoa' Programme for Centres of Excellence in R&D of the Spanish Ministry of Science and Innovation (CEX2020-001039-S). L.L thanks POSTDOC_DICYT 022342AP_Postdoc, Vicerrectoria de Investigacion, Desarrollo e Innovacion USACH.

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