Chiral Canoe-like Pd0 or Pt0 Alloyed Copper Alkynyl Nanoclusters Display Near-infrared Luminescence
Jun-Jie Fang, Zheng Liu, Zhi-Yi Wang, Yun-Peng Xie*, Xing Lu*
Angew. Chem. Int. Ed. 2024.
https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202401206
Abstract
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.
