In Situ Two-Phase Ligand Exchange: A New Method for the Synthesis of Alloy Nanoclusters with Precise Atomic Structures

A new method termed "in situ two-phase ligand exchange" was developed to obtain alloy nanoclusters. With this approach, a series of alloy nanoclusters were obtained for the first time, including Au₂₀Ag₁(SR)₁₅, Au21-xAgx(SR)₁₅ (x = 4-8), Au21-xCux(SR)₁₅ (x = 0, 1), and Au21-xCux(SR)₁₅ (x = 2-5) (R = tert-butyl). Interestingly, single-crystal X-ray crystallography (SC-XRD) shows that their frameworks are all alike except for Au21-xCux(SR)₁₅ (x = 2-5), indicating that more Cu dopants alter the structure. Au21-xCux(SR)₁₅ (x = 2-5) exhibits a significantly different configuration. The optical absorption spectra of these bimetal nanoclusters (NCs) show distinct characteristic peaks, indicating that the metal-doping remarkably affects the electronic structure of NCs. The DFT calculations were also employed for determination of NC 1-3 frameworks and understanding their optical properties.