Chiral Canoe‐Like Pd0 or Pt0 Alloyed Copper Alkynyl Nanoclusters Display Near‐Infrared Luminescence

Alloying nanoclusters (NCs) has emerged as a widely explored and versatile strategy for tailoring tunable properties, facilitating in‐depth atomic‐level investigations of structure‐property correlations. In this study, we have successfully synthesized six atomically precise copper NCs alloyed with G...

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Published in:Angewandte Chemie International Edition 2024-05, Vol.63 (20), p.e202401206-n/a
Main Authors: Fang, Jun‐Jie, Liu, Zheng, Wang, Zhi‐Yi, Xie, Yun‐Peng, Lu, Xing
Format: Article
Language:English
Subjects:
alkynyl copper nanocluster
alloy
Alloying
atomically precise
Chirality
Copper
Copper base alloys
Halogens
Heavy metals
Ligands
Luminescence
Nanoclusters
near-infrared luminescence
Optical properties
Palladium
Photoluminescence
Photons
Platinum
racemate
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Summary:Alloying nanoclusters (NCs) has emerged as a widely explored and versatile strategy for tailoring tunable properties, facilitating in‐depth atomic‐level investigations of structure‐property correlations. In this study, we have successfully synthesized six atomically precise copper NCs alloyed with Group 10 metals (Pd or Pt). Notably, the Pd0 or Pt0 atom situated at the center of the distorted hexagonal antiprism Pd0/Pt0@Cu12 cage, coordinated with twelve Cu+ and two tBuC≡C− ligands. Moreover, ligand exchange strategies demonstrated the potential for Cl− and Br− to replace one or two alkynyl ligands positioned at the top or side of the NCs. The chirality exhibited by these racemic NCs is primarily attributed to the involvement of halogens and a chiral (Pd/Pt)@Cu18 skeleton. Furthermore, all the NCs exhibit near‐infrared (NIR) luminescence, characterized by emission peaks at 705–755 nm, lifetimes ranging from 6.630 to 9.662 μs, and absolute photoluminescence quantum yields (PLQYs) of 1.75 %–2.52 % in their crystalline state. The experimental optical properties of these NCs are found to be in excellent agreement with the results of theoretical calculations. These alloy NCs not only offer valuable insights into the synthesis of Pd0/Pt0‐Cu alloy NCs, but also bridge the gap in understanding the structure‐luminescence relationships of Pd0/Pt0‐Cu molecules. Six racemic copper nanoclusters (NCs) alloyed with Pd0 or Pt0 were synthesized, showing a distorted hexagonal antiprism Pd0/Pt0@Cu12 cage. Cl− and Br− can replace one or two alkynyl ligands through ligand exchange. All the NCs exhibit near‐infrared (NIR) luminescence with emission peaks (705–755 nm), lifetimes (6.630–9.662 μs), and absolute quantum yields (1.75 %–2.52 %) in their crystalline state.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202401206