Hidalgo-Rosa, YoanSantoyo-Flores, JuliánTreto-Suárez, Manuel A.Schott, EduardoPáez-Hernández, DayánZarate, Ximena2024-12-032024-12-032023-04-27Journal of Luminescence, Vol. 260, N° 119896, (2023) p. 1-7.0022-2313http://hdl.handle.net/20.500.12254/3969The 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.enAtribución-NoComercial-CompartirIgual 3.0 Chile (CC BY-NC-SA 3.0 CL)Luminescence sensitizationCASSCFOrganic ligandsLuminescence sensitizationCASSCFOrganic ligandsArtículohttps://orcid.org/0000-0002-1391-435Xhttps://doi.org/10.1016/j.jlumin.2023.1198961872-7883