AI Article Synopsis
- Recently discovered chromium(0) and manganese(I) complexes show luminescence through metal-to-ligand charge transfer (MLCT) excited states, which could lead to new applications.
- These complexes, using chelating isocyanide ligands, demonstrate MLCT lifetimes approaching nanoseconds at room temperature in solution.
- Although current luminescence yields are low compared to established compounds like ruthenium(II) polypyridines, the findings offer strategies to improve luminescent properties in first-row transition metal complexes.
Article Abstract
In this Frontier article, recently discovered chromium(0) and manganese(I) complexes emitting from metal-to-ligand charge transfer (MLCT) excited states are highlighted. Chelating isocyanide ligands give access to this new class of 3d emitters with MLCT lifetimes in (or close to) the nanosecond regime in solution at room temperature. Although the so far achievable luminescence quantum yields in these open-shell complexes are yet comparatively low, the photophysical properties of the new chromium(0) and manganese(I) isocyanides are reminiscent of those of well-known ruthenium(II) polypyridines. Our findings provide insight into how undesired nonradiative MLCT deactivation in 3d complexes can be counteracted, and they seem therefore relevant for the further development of new luminescent first-row transition metal complexes based on iron(II) and cobalt(III) in addition to chromium(0) and manganese(I).
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| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8787763 | PMC |
| http://dx.doi.org/10.1039/d1dt03763c | DOI Listing |
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Controlling the Photophysical Properties of a Series of Isostructural d Complexes Based on Cr, Mn, and Fe.
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February 2024
Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland.
Development of first-row transition metal complexes with similar luminescence and photoredox properties as widely used Ru polypyridines is attractive because metals from the first transition series are comparatively abundant and inexpensive. The weaker ligand field experienced by the valence d-electrons of first-row transition metals challenges the installation of the same types of metal-to-ligand charge transfer (MLCT) excited states as in precious metal complexes, due to rapid population of energetically lower-lying metal-centered (MC) states. In a family of isostructural tris(diisocyanide) complexes of the 3d metals Cr, Mn, and Fe, the increasing effective nuclear charge and ligand field strength allow us to control the energetic order between the MLCT and MC states, whereas pyrene decoration of the isocyanide ligand framework provides control over intraligand (IL) states.
View Article and Find Full Text PDFLuminescent chromium(0) and manganese(I) complexes.
Dalton Trans
January 2022
Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland.
Article Synopsis
- Recently discovered chromium(0) and manganese(I) complexes show luminescence through metal-to-ligand charge transfer (MLCT) excited states, which could lead to new applications.
- These complexes, using chelating isocyanide ligands, demonstrate MLCT lifetimes approaching nanoseconds at room temperature in solution.
- Although current luminescence yields are low compared to established compounds like ruthenium(II) polypyridines, the findings offer strategies to improve luminescent properties in first-row transition metal complexes.
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