A manganese(I) complex with a 190 ns metal-to-ligand charge transfer lifetime

Abstract Application of photoactive transition metal complexes in lighting, imaging, sensing, and photocatalysis is usually based on the triplet metal-to-ligand charge transfer (3MLCT) excited state of precious metal complexes with 4/5d6 valence electron configurations. These photocatalysts exhibit...

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Main Authors: Sandra Kronenberger, Robert Naumann, Christoph Förster, Nathan R. East, Jan Klett, Katja Heinze
Format: Article
Language:English
Published: Nature Portfolio 2025-08-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-63225-4
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author Sandra Kronenberger
Robert Naumann
Christoph Förster
Nathan R. East
Jan Klett
Katja Heinze
author_facet Sandra Kronenberger
Robert Naumann
Christoph Förster
Nathan R. East
Jan Klett
Katja Heinze
author_sort Sandra Kronenberger
collection DOAJ
description Abstract Application of photoactive transition metal complexes in lighting, imaging, sensing, and photocatalysis is usually based on the triplet metal-to-ligand charge transfer (3MLCT) excited state of precious metal complexes with 4/5d6 valence electron configurations. These photocatalysts exhibit excited state lifetimes exceeding hundreds of nanoseconds. Simple 3d6 transition metal complexes containing abundant metals exhibit lifetimes below 1–2 nanoseconds, and they require multistep ligand syntheses mitigating large-scale implementation. We report that a commercially available bis(imidazolium) pyridine pro-ligand [H2pbmi]2+ and a manganese(II) salt yield the tetracarbene manganese(I) complex [Mn(pbmi)2]+. This complex phosphoresces at room temperature in fluid solution from a 3MLCT state with a lifetime of 190 ns. In combination with the reversible [Mn(pbmi)2]2+/+ process, this translates to an excited state capable of reducing benzophenone. Combination of manganese(I) with rigid carbene/pyridine ligands expands key strategies for photoactive 3d6 metal complexes of earth-abundant metals with 3MLCT lifetimes rivalling those of precious metals and providing a conceptual starting point for a sustainable photochemistry.
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spelling doaj-art-c8596adc81c041969cb70ae21144c7592025-08-24T11:39:35ZengNature PortfolioNature Communications2041-17232025-08-0116111110.1038/s41467-025-63225-4A manganese(I) complex with a 190 ns metal-to-ligand charge transfer lifetimeSandra Kronenberger0Robert Naumann1Christoph Förster2Nathan R. East3Jan Klett4Katja Heinze5Department of Chemistry, Johannes Gutenberg University MainzDepartment of Chemistry, Johannes Gutenberg University MainzDepartment of Chemistry, Johannes Gutenberg University MainzDepartment of Chemistry, Johannes Gutenberg University MainzDepartment of Chemistry, Johannes Gutenberg University MainzDepartment of Chemistry, Johannes Gutenberg University MainzAbstract Application of photoactive transition metal complexes in lighting, imaging, sensing, and photocatalysis is usually based on the triplet metal-to-ligand charge transfer (3MLCT) excited state of precious metal complexes with 4/5d6 valence electron configurations. These photocatalysts exhibit excited state lifetimes exceeding hundreds of nanoseconds. Simple 3d6 transition metal complexes containing abundant metals exhibit lifetimes below 1–2 nanoseconds, and they require multistep ligand syntheses mitigating large-scale implementation. We report that a commercially available bis(imidazolium) pyridine pro-ligand [H2pbmi]2+ and a manganese(II) salt yield the tetracarbene manganese(I) complex [Mn(pbmi)2]+. This complex phosphoresces at room temperature in fluid solution from a 3MLCT state with a lifetime of 190 ns. In combination with the reversible [Mn(pbmi)2]2+/+ process, this translates to an excited state capable of reducing benzophenone. Combination of manganese(I) with rigid carbene/pyridine ligands expands key strategies for photoactive 3d6 metal complexes of earth-abundant metals with 3MLCT lifetimes rivalling those of precious metals and providing a conceptual starting point for a sustainable photochemistry.https://doi.org/10.1038/s41467-025-63225-4
spellingShingle Sandra Kronenberger
Robert Naumann
Christoph Förster
Nathan R. East
Jan Klett
Katja Heinze
A manganese(I) complex with a 190 ns metal-to-ligand charge transfer lifetime
Nature Communications
title A manganese(I) complex with a 190 ns metal-to-ligand charge transfer lifetime
title_full A manganese(I) complex with a 190 ns metal-to-ligand charge transfer lifetime
title_fullStr A manganese(I) complex with a 190 ns metal-to-ligand charge transfer lifetime
title_full_unstemmed A manganese(I) complex with a 190 ns metal-to-ligand charge transfer lifetime
title_short A manganese(I) complex with a 190 ns metal-to-ligand charge transfer lifetime
title_sort manganese i complex with a 190 ns metal to ligand charge transfer lifetime
url https://doi.org/10.1038/s41467-025-63225-4
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