The geometric and electronic structures of a Ag13Cu10(SAdm)12X3 nanocluster

Abstract

Herein, we report the synthesis and total structure of a Cu-rich alloy nanocluster protected by twelve adamantanethiolate ligands, i.e., [Ag₁₃Cu₁₀(SAdm)₁₂]X₃ (–SAdm = SC₁₀H₁₅, X = counterion), which was confirmed by single-crystal X-ray structure determination and electrospray ionization mass spectrometry (ESI-MS). X-ray crystallographic analysis indicated that [Ag₁₃Cu₁₀(SAdm)₁₂]X₃ consisted of an icosahedral Ag₁₃ core, covered by a cage-like shell of Cu₁₀(SAdm)₁₂. Furthermore, density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations on the geometric and electronic structures and KS orbitals and UV-vis spectroscopy were performed on the model [Ag₁₃Cu₁₀(SMe)₁₂]³⁺ and its monometallic analog [Ag₂₃(SMe)₁₂]³⁺. This work will deepen the understanding of core–shell Ag–Cu alloy nanoclusters.