Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 9, Pages 4551-4554Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202012921
Keywords
metal clusters; nanoparticles; photoluminescence; platinum; silver
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Funding
- JST ERATO, Japan [JPMJER1503]
- JST PRESTO, Japan [JPMJPR1511]
- JSPS KAKENHI [JP 19J14680, JP 19H02535, 19J14680]
- Cooperative Research Program of Network Joint Research Center for Materials and Devices
- Grants-in-Aid for Scientific Research [19J14680] Funding Source: KAKEN
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Controversy surrounds the roles of metal core and shell in photoluminescence of ligand-protected metal nanoclusters. The inclusion of silver ions in a platinum-thiolate complex led to a significant increase in photoluminescent quantum yield. DFT calculations showed that LUMO, with contributions from Ag s-orbital and Pt d-orbitals, played a critical role in suppressing structural distortion in the excited state.
There has been controversy surrounding the roles of the metal core (metal-metal interaction) and the shell (metal-ligand interaction) in photoluminescence of ligand-protected metal nanoclusters. We have discovered aggregation-induced room-temperature phosphorescence of a platinum-thiolate complex and its silver ion inclusion complex (a silver-doped platinum sub-nanocluster). The inclusion of silver ion boosted the photoluminescent quantum yield by 18 times. Photophysical measurements indicate that the rate of nonradiative decay was slower for the silver-doped platinum sub-nanocluster. DFT calculations showed that the LUMO, which had the main contribution from Ag s-orbital and Pt d-orbitals, played a critical role in suppressing the structural distortion at the excited state. This work will hopefully stimulate more research on designing strategies based on molecular orbitals of atomicity-precise luminescent multimetallic nanoclusters.
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