Chiral Canoe-Like Pd or Pt 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 Group 10 metals (Pd or Pt). Notably, the Pd or Pt atom situated at the center of the distorted hexagonal antiprism Pd/Pt@Cu cage, coordinated with twelve Cu and two BuC≡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)@Cu 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 Pd/Pt-Cu alloy NCs, but also bridge the gap in understanding the structure-luminescence relationships of Pd/Pt-Cu molecules.