Tuning the sensitization pathway T1→ 5DJ in Eu-based MOF through modification of the antenna ligand: a theoretical approach via multiconfigurational quantum calculations

Vista sencilla de ítem
dc.contributor.authorHidalgo-Rosa, Yoan
dc.contributor.authorSantoyo-Flores, Julián
dc.contributor.authorTreto-Suárez, Manuel A.
dc.contributor.authorSchott, Eduardo
dc.contributor.authorPáez-Hernández, Dayán
dc.contributor.authorZarate, Ximena
dc.date.accessioned2024-12-03T19:03:54Z
dc.date.available2024-12-03T19:03:54Z
dc.date.issued2023-04-27
dc.description.abstractThe current study demonstrates the possibility of improving the efficiency of Eu3+ sensitization in an Eu-based MOF, labelled as EuL-R, by modifying the antenna ligand. The electronic structure of seven antenna ligand derivatives with the form R-4-(pyrimidin-5-yl) benzoic acid (L-R) ligand derivates was thoroughly examined in this research. Also, the most likely energy transfer channels for the sensitization pathway of Eu3+ ions in the EuL-R systems (R: CH3, –OH, –SH and –NH2) was studied. The efficiency in the intersystem crossing (ISC) process from S1 to T1 in the antenna make plausible a subsequent energy transfer to the emissive state in the Eu3+. This process was studied via multireference CASSCF/NEVPT2 calculations due to the multiconfigurational character of Eu3+ ions. Based on Latva and Reindhout's empirical rules, the 4-(2-(thiophen-2-yl)pyrimidin-5-yl)benzoic acid (L6) was chosen as efficient antenna for the sensitization process in this system. In conclusion, it was discovered that including the thiophenyl group at the L antenna (L6), increased the energy gaps S1→T1 and T1→5DJ (Eu3+) to an optimal range for the ISC and subsequent energy transfer. Finally, a deeply understanding of the sensitization and emission mechanisms was possible from the excited-state dynamics analysis of the L6 antenna, via fluorescence, inter-system crossing (ISC), phosphorescence, and kF, kISC, and kP, rates calculations. This study therefore highlights the importance of a thorough theoretical procedure via a robust quantum mechanical tool to guide the development of novel luminescent lanthanide-based MOFs.es
dc.identifier.citationJournal of Luminescence, Vol. 260, N° 119896, (2023) p. 1-7.
dc.identifier.doihttps://doi.org/10.1016/j.jlumin.2023.119896
dc.identifier.issn0022-2313
dc.identifier.issne1872-7883
dc.identifier.orcidhttps://orcid.org/0000-0002-1391-435X
dc.identifier.urihttp://hdl.handle.net/20.500.12254/3969
dc.language.isoenes
dc.publisherElsevier
dc.rightsAtribución-NoComercial-CompartirIgual 3.0 Chile (CC BY-NC-SA 3.0 CL)
dc.rights.urihttp://creativecommons.org/licenses/by-nc-sa/3.0/cl/
dc.subjectLuminescence sensitization
dc.subjectCASSCF
dc.subjectOrganic ligands
dc.subject.otherLuminescence sensitizationes
dc.subject.otherCASSCFes
dc.subject.otherOrganic ligandses
dc.titleTuning the sensitization pathway T1→ 5DJ in Eu-based MOF through modification of the antenna ligand: a theoretical approach via multiconfigurational quantum calculations
dc.typeArtículoes
Archivos
Bloque original
Mostrando 1 - 1 de 1
Miniatura
Nombre:
turing the sensitization Yoan Hidalgo-1.pdf
Tamaño:
252.93 KB
Formato:
Adobe Portable Document Format
Descripción:
Texto referencial
Descargar
Bloque de licencias
Mostrando 1 - 1 de 1
No hay miniatura disponible
Nombre:
license.txt
Tamaño:
347 B
Formato:
Item-specific license agreed upon to submission
Descripción:
Descargar
Colecciones
Artículos de Revistas