Curved nanographenes: Multiple emission, thermally activated delayed fluorescence, and non-radiative decay

The intriguing and rich photophysical properties of three curved nanographenes (CNG 6, 7, and 8) are investigated by time-resolved and temperature-dependent photoluminescence (PL) spectroscopy. CNG 7 and 8 exhibit dual fluorescence, as well as dual phosphorescence at low temperature in the main PL b...

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Detalhes bibliográficos
Autores: Ramírez-Barroso, Sergio, Romeo-Gella, Fernando, Fernández-García, Jesús M., Feng, Siyang, Martínez Fernández, Lara, García-Fresnadillo, David, Corral Pérez, Inés, Martín, Nazario, Wannemacher, Reinhold
Formato: artículo
Fecha de publicación:2023
País:España
Recursos:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/708719
Acesso em linha:http://hdl.handle.net/10486/708719
https://dx.doi.org/10.1002/adma.202212064
Access Level:acceso abierto
Palavra-chave:Curved nanographenes
Multiple emission
Phosphorescence
Thermally activated delayed fluorescence (TADF)
Química
Descrição
Resumo:The intriguing and rich photophysical properties of three curved nanographenes (CNG 6, 7, and 8) are investigated by time-resolved and temperature-dependent photoluminescence (PL) spectroscopy. CNG 7 and 8 exhibit dual fluorescence, as well as dual phosphorescence at low temperature in the main PL bands. In addition, hot bands are detected in fluorescence as well as phosphorescence, and, in the narrow temperature range of 100–140 K, thermally activated delayed fluorescence (TADF) with lifetimes on the millisecond time-scale is observed. These findings are rationalized by quantum-chemical simulations, which predict a single minimum of the S1 potential of CNG 6, but two S1 minima for CNG 7 and CNG 8, with considerable geometric reorganization between them, in agreement with the experimental findings. Additionally, a higher-lying S2 minimum close to S1 is optimized for the three CNG, from where emission is also possible due to thermal activation and, hence, non-Kasha behavior. The presence of higher-lying dark triplet states close to the S1 minima provides mechanistic evidence for the TADF phenomena observed. Non-radiative decay of the T1 state appears to be thermally activated with activation energies of roughly 100 meV and leads to disappearance of phosphorescence and TADF at T > 140 K