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

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.

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 ^t 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)@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.

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