| Texto completo | |
| Autor(es): |
Saraiva, Leonardo F.
;
Beltrame, Ariane C. F.
;
Bispo-Jr, Airton G.
;
Canisares, Felipe S. M.
;
Neto, Albano N. Carneiro
;
Moura Jr, Renaldo T.
;
Kraka, E.
;
Lima, Sergio A. M.
;
Pires, Ana M.
Número total de Autores: 9
|
| Tipo de documento: | Artigo Científico |
| Fonte: | ACS OMEGA; v. 10, n. 28, p. 13-pg., 2025-07-12. |
| Resumo | |
The elucidation of the mechanisms governing the photophysical properties of trivalent lanthanide (LnIII) complexes embedded in polymeric matrices, such as poly(methyl) methacrylate (PMMA) and polyvinylidene fluoride (PVDF), is challenging due to their intricate composite nature. Although theoretical modeling offers insights into film luminescence, conventional computational strategies face significant limitations. Given the large-scale nature of these systems, which encompass thousands of atoms, full-scale quantum mechanical (QM) simulations are impractical. Existing methodologies often integrate molecular mechanics (MM) with QM, yet such hybrid frameworks introduce inaccuracies in excited-state calculations. To address these challenges, this study proposes a multilevel computational protocol employing a hybrid QM/QM approach. Density functional theory (DFT) was used for the [Eu(dbm)4]- complex (dbm = 1,3-diphenyl-1,3-propanedione), while the polymeric environment was treated using the GFNn-xTB method. The protocol demonstrated strong agreement between experimental and theoretical emission quantum yields (QY) for both the isolated complex and [Eu(dbm)4]-/PMMA or PVDF films. Our findings revealed that angular and length distortions in the Eu-O bonds within PVDF were induced by increased packing around the complex, impacting the ligand-EuIII energy transfer by elevating the triplet state energy. These results underscore the predictive capabilities of the hybrid QM/QM strategy, offering a robust alternative for deciphering opto-structural relationships in LnIII-based polymeric films. (AU) | |
| Processo FAPESP: | 23/05718-9 - Filmes luminescentes multifuncionais baseados em down-shifting e up-conversion para aplicação em anti-falsificação e micro-LEDs recobertos para tecnologia de displays |
| Beneficiário: | Leonardo Figueiredo Saraiva |
| Modalidade de apoio: | Bolsas no Brasil - Doutorado Direto |
| Processo FAPESP: | 23/16684-8 - Plataformas multifuncionais compostas por híbridos inorgânico-orgânico UCNPS@SiO2-Ln3+-Ir3+ para sensoriamento, imageamento celular e geração de oxigênio singleto pelo processo de upconversion |
| Beneficiário: | Felipe da Silva Manrique Canisares |
| Modalidade de apoio: | Bolsas no Brasil - Pós-Doutorado |