Efficient Triplet‐Triplet Annihilation Upconversion Sensitized by a Chromium(III) Complex via an Underexplored Energy Transfer Mechanism

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  • Cui Wang
    Division Biophotonics Federal Institute for Materials Research and Testing (BAM) Richard-Willstätter-Strasse 11 12489 Berlin Germany
  • Florian Reichenauer
    Department of Chemistry Johannes Gutenberg University of Mainz Duesbergweg 10–14 55128 Mainz Germany
  • Winald R. Kitzmann
    Department of Chemistry Johannes Gutenberg University of Mainz Duesbergweg 10–14 55128 Mainz Germany
  • Christoph Kerzig
    Department of Chemistry Johannes Gutenberg University of Mainz Duesbergweg 10–14 55128 Mainz Germany
  • Katja Heinze
    Department of Chemistry Johannes Gutenberg University of Mainz Duesbergweg 10–14 55128 Mainz Germany
  • Ute Resch‐Genger
    Division Biophotonics Federal Institute for Materials Research and Testing (BAM) Richard-Willstätter-Strasse 11 12489 Berlin Germany

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<jats:title>Abstract</jats:title><jats:p>Sensitized triplet‐triplet annihilation upconversion (sTTA‐UC) mainly relies on precious metal complexes thanks to their high intersystem crossing (ISC) efficiencies, excited state energies, and lifetimes, while complexes of abundant first‐row transition metals are only rarely utilized and with often moderate UC quantum yields. [Cr(bpmp)<jats:sub>2</jats:sub>]<jats:sup>3+</jats:sup> (bpmp=2,6‐bis(2‐pyridylmethyl)pyridine) containing earth‐abundant chromium possesses an absorption band suitable for green light excitation, a doublet excited state energy matching the triplet energy of 9,10‐diphenyl anthracene (DPA), a close to millisecond excited state lifetime, and high photostability. Combined ISC and doublet‐triplet energy transfer from excited [Cr(bpmp)<jats:sub>2</jats:sub>]<jats:sup>3+</jats:sup> to DPA gives <jats:sup>3</jats:sup>DPA with close‐to‐unity quantum yield. TTA of <jats:sup>3</jats:sup>DPA furnishes green‐to‐blue UC with a quantum yield of 12.0 % (close to the theoretical maximum). Sterically less‐hindered anthracenes undergo a [4+4] cycloaddition with [Cr(bpmp)<jats:sub>2</jats:sub>]<jats:sup>3+</jats:sup> and green light.</jats:p>

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