Atomically Engineered Trimetallic Nanoclusters Toward Enhanced Photoluminescence and Photoinitiation Activity.

Liu, Xu; Tang, Jin; Zhao, Fangming; Zhou, Meng; Ye, Siyang; Hong, Daocheng; Tian, Yuxi; Zhao, Yue et al. · Adv Mater · 2025

basic_science · Level V

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Abstract

Precise doping is of vital significance for atomic engineering and the establishment of structure-property relationships in nanocluster (NC) chemistry. Herein, two novel trimetallic MAu<sub>18</sub>Cd<sub>3</sub> (M = Pd/Pt) NCs that are derived from M-doped Au<sub>25</sub> templates of MAu<sub>24</sub> are reported, in which the central doping of M atom and the surface-motif doping of Cd atoms are concurrently achieved. Compared to the original templates, Cd-induced surface engineering enhances the rigidity of the structural framework and enlarges the HOMO-LUMO gaps of the MAu<sub>18</sub>Cd<sub>3</sub>, significantly improving photoluminescent efficiency by suppressing nonradiative relaxation. The critical role of the central M (Pd/Pt) dopant in photoluminescence, which regulates the rate of radiative decay of excited-state electrons, has also been substantiated. More notably, the doped case of PtAu<sub>18</sub>Cd<sub>3</sub> exhibits excellent photoinitiation activity in 3D two-photon printing with a high resolution of ≈140 nm, which may be attributed to the prolonged excited state. Overall, this work provides a generalized routine for the precise synthesis of multi-metal NCs with concurrent enhancements in photoluminescence and photoinitiation activity, which is expected to stimulate further research for the design and preparation of multi-functional, multi-metal NCs.