Impact of ligand-centered excited states on luminescence sensitization in Pr3+ complexes with β-diketones

• Published in: Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy Vol. 260
• Main Authors: Korshunov, V.M., Metlin, M.T., Ambrozevich, S.A., Golovanov, I.S., Gontcharenko, V.E., Selyukov, A.S., Taydakov, I.V.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 05.11.2021
• Subjects: 1,10-phenanthroline; 1,3-diketones; Luminescence; Near-infrared emission; Pr(III) complexes; Pyrazole; 1,10-phenanthroline; Pr(III) complexes; 1,3-diketones; Pyrazole; Luminescence; Near-infrared emission
• ISSN: 1386-1425
• DOI: 10.1016/j.saa.2021.119863

[Display omitted] •Novel Pr3+ complexes with 1,3-diketonate ligands were synthesized.•Two ligand-to-ligand charge transfer states of different types were found.•LLCT states can transfer energy to the 3P0 and 3P1 levels of Pr3+. In this study, two novel Pr3+ complexes with different 1,3-diketonate ligands were synthesized and investigated. To study the effect of the ancillary ligand on the energy transfer mechanisms in the complexes, a phenanthroline ligand was introduced. To take into account the influence of the ligand environment composed of different ligands on the energy transfer and relaxation processes, we compared the synthesized compounds with a similar complex containing the phenanthroline ligand. The spectroscopic studies in the visible and near-infrared spectral regions were supplemented with DFT and TD-DFT calculations. We found two ligand-to-ligand charge transfer (LLCT) states, with one state corresponding to energy transfer between 1,3-diketones and the other – to energy transfer from the 1,3-diketone to the phenanthroline motif. It was demonstrated that optical excitation via the latter channel leads to a fourfold increase in the luminescence quantum yield as compared with excitation via the π-π∗ transitions in 1,3-diketones. Moreover, both LLCT states provide sensitization of the Pr3+ luminescence involving the 3P0 and 3P1 levels.