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

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dc.contributor.authorHidalgo-Rosa, Yoan
dc.contributor.authorSantoyo-Flores, Julian
dc.contributor.authorTreto-Suarez, Manuel A.
dc.contributor.authorSchott, Eduardo
dc.contributor.authorPaez-Hernandez, Dayan
dc.contributor.authorZarate, Ximena
dc.date.accessioned2025-01-20T20:10:55Z
dc.date.available2025-01-20T20:10:55Z
dc.date.issued2023
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 me-chanical tool to guide the development of novel luminescent lanthanide-based MOFs.
dc.fuente.origenWOS
dc.identifier.doi10.1016/j.jlumin.2023.119896
dc.identifier.eissn1872-7883
dc.identifier.issn0022-2313
dc.identifier.urihttps://doi.org/10.1016/j.jlumin.2023.119896
dc.identifier.urihttps://repositorio.uc.cl/handle/11534/92106
dc.identifier.wosidWOS:000999125400001
dc.language.isoen
dc.revistaJournal of luminescence
dc.rightsacceso restringido
dc.subjectLuminescence sensitization
dc.subjectCASSCF
dc.subjectOrganic ligands
dc.subject.ods07 Affordable and Clean Energy
dc.subject.odspa07 Energía asequible y no contaminante
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.typeartículo
dc.volumen260
sipa.indexWOS
sipa.trazabilidadWOS;2025-01-12
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