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Nature of the Ligand-Centered Triplet State in Gd3+ ß-Diketonate Complexes as Revealed by Time-Resolved EPR Spectroscopy and DFT Calculations.
Carlotto, Silvia; Babetto, Luca; Bortolus, Marco; Carlotto, Alice; Rancan, Marzio; Bottaro, Gregorio; Armelao, Lidia; Carbonera, Donatella; Casarin, Maurizio.
Afiliación
  • Carlotto S; Department of Chemistry, University of Padova, via F. Marzolo 1, 35131 Padova, Italy.
  • Babetto L; Institute of Condensed Matter Chemistry and Technologies for Energy (ICMATE), National Research Council (CNR), c/o Department of Chemistry, University of Padova, via F. Marzolo 1, 35131 Padova, Italy.
  • Bortolus M; Department of Chemistry, University of Padova, via F. Marzolo 1, 35131 Padova, Italy.
  • Carlotto A; Department of Chemistry, University of Padova, via F. Marzolo 1, 35131 Padova, Italy.
  • Rancan M; Department of Chemistry, University of Padova, via F. Marzolo 1, 35131 Padova, Italy.
  • Bottaro G; Institute of Condensed Matter Chemistry and Technologies for Energy (ICMATE), National Research Council (CNR), c/o Department of Chemistry, University of Padova, via F. Marzolo 1, 35131 Padova, Italy.
  • Armelao L; Institute of Condensed Matter Chemistry and Technologies for Energy (ICMATE), National Research Council (CNR), c/o Department of Chemistry, University of Padova, via F. Marzolo 1, 35131 Padova, Italy.
  • Carbonera D; Department of Chemistry, University of Padova, via F. Marzolo 1, 35131 Padova, Italy.
  • Casarin M; Department of Chemical Sciences and Technology of Materials (DSCTM), National Research Council (CNR), Piazzale A. Moro 7, 00185 Roma, Italy.
Inorg Chem ; 60(20): 15141-15150, 2021 Oct 18.
Article en En | MEDLINE | ID: mdl-34612628
A series of Gd3+ complexes (Gd1-Gd3) with the general formula GdL3(EtOH)2, where L is a ß-diketone ligand with polycyclic aromatic hydrocarbon substituents of increasing size (1-3), was studied by combining time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy and DFT calculations to rationalize the anomalous spectroscopic behavior of the bulkiest complex (Gd3) through the series. Its faint phosphorescence band is observed only at 80 K and it is strongly red-shifted (∼200 nm) from the intense fluorescence band. Moreover, the TR-EPR spectral analysis found that triplet levels of 3/Gd3 are effectively populated and have smaller |D| values than those of the other compounds. The combined use of zero-field splitting and spin density delocalization calculations, together with spin population analysis, allows us to explain both the large red shift and the low intensity of the phosphorescence band observed for Gd3. The large red shift is determined by the higher delocalization degree of the wavefunction, which implies a larger energy gap between the excited S1 and T1 states. The low intensity of the phosphorescence is due to the presence of C-H groups which favor non-radiative decay. These groups are present in all complexes; nevertheless, they have a relevant spin density only in Gd3. The spin population analysis on NaL models, in which Na+ is coordinated to a deprotonated ligand, mimicking the coordinative environment of the complex, confirms the outcomes on the free ligands.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Inorg Chem Año: 2021 Tipo del documento: Article País de afiliación: Italia Pais de publicación: Estados Unidos
Texto completo
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Inorg Chem Año: 2021 Tipo del documento: Article País de afiliación: Italia Pais de publicación: Estados Unidos