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A Vanadium(III) Complex with Blue and NIR-II Spin-Flip Luminescence in Solution

  • Matthias Dorn
    Matthias Dorn
    Department of Chemistry, Johannes Gutenberg University of Mainz, Duesbergweg 10-14, Mainz 55128, Germany
  • Jens Kalmbach
    Jens Kalmbach
    Institute of Inorganic Chemistry, University of Tübingen, Auf der Morgenstelle 18, Tübingen 72076, Germany
  • Pit Boden
    Pit Boden
    Department of Chemistry and Research Center Optimas, TU Kaiserslautern, Erwin-Schrödinger-Straße, Kaiserslautern 67663, Germany
    More by Pit Boden
  • Ayla Päpcke
    Ayla Päpcke
    Institute for Physics and Department of Life, Light and Matter, University of Rostock, Rostock 18051, Germany
    More by Ayla Päpcke
  • Sandra Gómez
    Sandra Gómez
    Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna, Währinger Straße 17, Vienna 1090, Austria
  • Christoph Förster
    Christoph Förster
    Department of Chemistry, Johannes Gutenberg University of Mainz, Duesbergweg 10-14, Mainz 55128, Germany
  • Felix Kuczelinis
    Felix Kuczelinis
    Department of Chemistry, Johannes Gutenberg University of Mainz, Duesbergweg 10-14, Mainz 55128, Germany
  • Luca M. Carrella
    Luca M. Carrella
    Department of Chemistry, Johannes Gutenberg University of Mainz, Duesbergweg 10-14, Mainz 55128, Germany
  • Laura A. Büldt
    Laura A. Büldt
    Institute of Inorganic Chemistry, University of Tübingen, Auf der Morgenstelle 18, Tübingen 72076, Germany
  • Nicolas H. Bings
    Nicolas H. Bings
    Department of Chemistry, Johannes Gutenberg University of Mainz, Duesbergweg 10-14, Mainz 55128, Germany
  • Eva Rentschler
    Eva Rentschler
    Department of Chemistry, Johannes Gutenberg University of Mainz, Duesbergweg 10-14, Mainz 55128, Germany
  • Stefan Lochbrunner
    Stefan Lochbrunner
    Institute for Physics and Department of Life, Light and Matter, University of Rostock, Rostock 18051, Germany
  • Leticia González
    Leticia González
    Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna, Währinger Straße 17, Vienna 1090, Austria
  • Markus Gerhards*
    Markus Gerhards
    Department of Chemistry and Research Center Optimas, TU Kaiserslautern, Erwin-Schrödinger-Straße, Kaiserslautern 67663, Germany
    *[email protected]
  • Michael Seitz*
    Michael Seitz
    Institute of Inorganic Chemistry, University of Tübingen, Auf der Morgenstelle 18, Tübingen 72076, Germany
    *[email protected]
  • , and 
  • Katja Heinze*
    Katja Heinze
    Department of Chemistry, Johannes Gutenberg University of Mainz, Duesbergweg 10-14, Mainz 55128, Germany
    *[email protected]
    More by Katja Heinze
Cite this: J. Am. Chem. Soc. 2020, 142, 17, 7947–7955
Publication Date (Web):April 10, 2020
https://doi.org/10.1021/jacs.0c02122
Copyright © 2020 American Chemical Society

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    Abstract

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    Luminescence from Earth-abundant metal ions in solution at room temperature is a very challenging objective due to the intrinsically weak ligand field splitting of first-row transition metal ions, which leads to efficient nonradiative deactivation via metal-centered states. Only a handful of 3dn metal complexes (n ≠ 10) show sizable luminescence at room temperature. Luminescence in the near-infrared spectral region is even more difficult to achieve as further nonradiative pathways come into play. No Earth-abundant first-row transition metal complexes have displayed emission >1000 nm at room temperature in solution up to now. Here, we report the vanadium(III) complex mer-[V(ddpd)2][PF6]3 yielding phosphorescence around 1100 nm in valeronitrile glass at 77 K as well as at room temperature in acetonitrile with 1.8 × 10–4% quantum yield (ddpd = N,N′-dimethyl-N,N′-dipyridine-2-ylpyridine-2,6-diamine). In addition, mer-[V(ddpd)2][PF6]3 shows very strong blue fluorescence with 2% quantum yield in acetonitrile at room temperature. Our comprehensive study demonstrates that vanadium(III) complexes with d2 electron configuration constitute a new class of blue and NIR-II luminophores, which complement the classical established complexes of expensive precious metals and rare-earth elements.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.0c02122.

    • Data of quantum chemical calculations, synthetic procedures, and analytical and spectroscopic data of [V(ddpd)2][PF6]3 (PDF)

    • X-ray crystallographic data for mer-[V(ddpd)2][PF6]3×3CH3CN (CIF)

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