4.8 Article

Single Platinum Atom Doping to Silver Clusters Enables Near-Infrared-to-Blue Photon Upconversion

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 6, Pages 2822-2827

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202013725

Keywords

intersystem crossing; ligand-protected metal clusters; superatoms; triplet sensitizers; triplet-triplet annihilation photon upconversion

Funding

  1. Sumitomo Foundation [170899]
  2. Rikkyo University Special Fund for Research [20K15110, 20K05653]

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This study investigated noble metal clusters as new NIR-absorbing sensitizers, finding that PtAg24(SR)(18) exhibits strong triplet-triplet annihilation upconversion (UC) emission.
Photon upconversion (UC) from near-infrared (NIR) to visible has been realized using singlet-to-triplet absorption of sensitizers, which are currently limited to osmium complexes and semiconductor nanocrystals. Motivated by the atomically precise tunability of electronic structure and photophysical properties of noble metal clusters, which often possess absorption bands that extend into the NIR region, we investigated MAg24(SR)(18) (M=Ag, Pt; SR=2,4-dimethylbenzenethiolate) clusters as a new NIR-absorbing sensitizer for triplet-triplet annihilation UC. Combined with a blue light emitter, the NIR excitation (lambda(ex)=785 nm) of Ag-25(SR)(18) results in no UC emission, while PtAg24(SR)(18) exhibits strong UC emission. This enhancement is primarily due to a significant increase in the intersystem crossing quantum yield of the cluster associated with the spin-orbit coupling enhancement in the M@Ag-12 core.

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