Boranil Chelates as Antennae for Ytterbium(III) Luminescence Sensitization

Five original ligands based on bipyridine and phenanthroline chelating units connected to boranil moieties are synthesized and characterized, including single-crystal X-ray diffraction. For classical boranil moieties, large absorption coefficients are observed, together with intense fluorescence. For sulfur-containing boranils, absorption coefficients and fluorescence quantum yields are smaller, but larger Stokes shifts are observed, together with singlet oxygen generation. These features are in line with the time-dependent density functional theory study, which also reproduces well the behavior of the yttrium(III) complexes; more specifically, the positioning of the ligand triplet states, which is in the range of 15,500–20,000 cm–1, as well as the larger spin–orbit coupling allowing better intersystem crossing for sulfur-containing boranils. In addition to ligand-based fluorescence, all five ytterbium complexes show near-infrared emission with quantum yields (ΦYbL) in the range of 0.0027–0.0040, lifetimes in the range of 8.8–11.4 μs, and brightness (B = ε·ΦLnL) in the range of 121–163 M–1·cm–1 (with 350 nm excitation).

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Publication Details

Journal
Inorganic Chemistry
Published
2026-05-21
DOI
https://doi.org/10.1021/acs.inorgchem.6c00187
Primary Topic
Lanthanide and Transition Metal Complexes
Type
article
Field-Weighted Citation Impact
0.00

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article

Boranil Chelates as Antennae for Ytterbium(III) Luminescence Sensitization

Guillaume Micouin, Ludmilla Verrieux, Lucie Norel, Emmanuel Baranger et al.
Inorganic Chemistry
Lanthanide and Transition Metal Complexes
article

Boranil Chelates as Antennae for Ytterbium(III) Luminescence Sensitization

Guillaume Micouin, Ludmilla Verrieux, Lucie Norel, Emmanuel Baranger, Olivier Galangau, Salauat R. Kiraev, Ákos Bányász, Yoann Fréroux, Stéphane Rigaut, Olivier Maury, Boris Le Guennic, Marie Cordier, Karine Costuas
article en

Abstract

Five original ligands based on bipyridine and phenanthroline chelating units connected to boranil moieties are synthesized and characterized, including single-crystal X-ray diffraction. For classical boranil moieties, large absorption coefficients are observed, together with intense fluorescence. For sulfur-containing boranils, absorption coefficients and fluorescence quantum yields are smaller, but larger Stokes shifts are observed, together with singlet oxygen generation. These features are in line with the time-dependent density functional theory study, which also reproduces well the behavior of the yttrium(III) complexes; more specifically, the positioning of the ligand triplet states, which is in the range of 15,500–20,000 cm–1, as well as the larger spin–orbit coupling allowing better intersystem crossing for sulfur-containing boranils. In addition to ligand-based fluorescence, all five ytterbium complexes show near-infrared emission with quantum yields (ΦYbL) in the range of 0.0027–0.0040, lifetimes in the range of 8.8–11.4 μs, and brightness (B = ε·ΦLnL) in the range of 121–163 M–1·cm–1 (with 350 nm excitation).

Inorganic Chemistry
Université Claude Bernard Lyon 1 (FR), École Normale Supérieure de Lyon (FR), Centre National de la Recherche Scientifique (FR), Lyon College (US), Institut Universitaire de France (FR), Institut des Sciences Chimiques de Rennes (FR), Université de Rennes (FR)
Agence Nationale de la Recherche, Institut Universitaire de France
Openalex Percentile: Top 11%
Lanthanide and Transition Metal Complexes
DOISourceOpenAlex
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