Visible Light-Harvesting Dinuclear Chromium(III) Complex with Anthracene-Based Phosphorescence for Photon Upconversion and Photocatalysis.
4 affiliations
- 1Department of Chemistry, University of Konstanz, Universitätsstraße 10, 78464Konstanz, Germany.
- 2Leibniz Institute of Photonic Technology, e. V. Jena, Albert-Einstein-Straße 9, 07745Jena, Germany.
- 3Institute of Inorganic Chemistry, University of Göttingen, Tammannstraße 4, 37077Göttingen, Germany.
- 4Leibniz Institute of Surface Engineering (IOM), Permoserstraße 15, 04318Leipzig, Germany.
Abstract
Luminescent 3d3 chromium(III) complexes are emerging as highly attractive, earth-abundant alternatives to precious 4d or 5d metal complexes in photophysical and photochemical applications. However, the Laporte-forbidden nature of their d-d transitions in the visible region severely hampers the light-harvesting efficiency of conventional photoactive CrIII complexes. To overcome this fundamental bottleneck, we anchored two anthracene-based antennas to the polypyridine ligands in a dinuclear CrIII complex, yielding the complex Cr2-An. The resulting energetically low-lying π-π* transition in the anthracene antenna enhances visible light absorption at 450 nm by a factor of 30 relative to the anthracene-free reference complex, Cr2-ref Both dimers exhibit ferromagnetic ground-state exchange interactions and display room temperature luminescence, albeit originating from different excited states. Specifically, Cr2-An exhibits anthracene-based phosphorescence with a lifetime of ∼150 ns in solution at room temperature, which is likely accessible via two pathways: direct intersystem crossing from the singlet excited state of the anthracene fragment, or intramolecular doublet-triplet energy transfer from the spin-flip excited states of the CrIII centers. These exceptional photophysical properties render Cr2-An an attractive photosensitizer for triplet-triplet annihilation upconversion (TTA-UC) and singlet oxygen-mediated oxidation reactions, delivering photocatalytic performance that surpasses the benchmark [Ru(bpy)3]Cl2 under visible-light irradiation. These findings offer a powerful molecular design strategy for bypassing the intrinsic optical limitations of first-row transition metals, opening new avenues for sustainable and efficient light energy conversion.
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BibTeX
@article{fritzler2026visible,
title = {{Visible Light-Harvesting Dinuclear Chromium(III) Complex with Anthracene-Based Phosphorescence for Photon Upconversion and Photocatalysis.}},
author = {Dennis Fritzler and Katharina L Deuter and Nikita Vashistha and Serhiy Demeshko and Michael Linseis and Pengyue Jin and Franc Meyer and Benjamin Dietzek-Ivanšić and Rainer F Winter and Cui Wang},
journal = {Journal of the American Chemical Society},
year = {2026},
month = oct,
doi = {10.1021/jacs.6c13239},
url = {https://europepmc.org/article/MED/42913597},
note = {CC BY},
}
RIS
TY - JOUR
TI - Visible Light-Harvesting Dinuclear Chromium(III) Complex with Anthracene-Based Phosphorescence for Photon Upconversion and Photocatalysis.
AU - Dennis Fritzler
AU - Katharina L Deuter
AU - Nikita Vashistha
AU - Serhiy Demeshko
AU - Michael Linseis
AU - Pengyue Jin
AU - Franc Meyer
AU - Benjamin Dietzek-Ivanšić
AU - Rainer F Winter
AU - Cui Wang
PY - 2026
DA - 2026/10/01
JO - Journal of the American Chemical Society
DO - 10.1021/jacs.6c13239
UR - https://europepmc.org/article/MED/42913597
AB - Luminescent 3d3 chromium(III) complexes are emerging as highly attractive, earth-abundant alternatives to precious 4d or 5d metal complexes in photophysical and photochemical applications. However, the Laporte-forbidden nature of their d-d transitions in the visible region severely hampers the light-harvesting efficiency of conventional photoactive CrIII complexes. To overcome this fundamental bottleneck, we anchored two anthracene-based antennas to the polypyridine ligands in a dinuclear CrIII complex, yielding the complex Cr2-An. The resulting energetically low-lying π-π* transition in the anthracene antenna enhances visible light absorption at 450 nm by a factor of 30 relative to the anthracene-free reference complex, Cr2-ref Both dimers exhibit ferromagnetic ground-state exchange interactions and display room temperature luminescence, albeit originating from different excited states. Specifically, Cr2-An exhibits anthracene-based phosphorescence with a lifetime of ∼150 ns in solution at room temperature, which is likely accessible via two pathways: direct intersystem crossing from the singlet excited state of the anthracene fragment, or intramolecular doublet-triplet energy transfer from the spin-flip excited states of the CrIII centers. These exceptional photophysical properties render Cr2-An an attractive photosensitizer for triplet-triplet annihilation upconversion (TTA-UC) and singlet oxygen-mediated oxidation reactions, delivering photocatalytic performance that surpasses the benchmark [Ru(bpy)3]Cl2 under visible-light irradiation. These findings offer a powerful molecular design strategy for bypassing the intrinsic optical limitations of first-row transition metals, opening new avenues for sustainable and efficient light energy conversion.
SN - 0002-7863
SN - 1520-5126
ER -