Abstract

AbstractThere 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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