LAUSR

Understanding the ligand effects in the nanocluster (NC) range is crucial for tailoring the properties. We herein report on the crystal structure of the Au15Ag3(SPhMe2)14 nanocluster. Compared with the previously reported Au15Au3(SC6H11)14 nanocluster, Au15Ag3(SPhMe2)14 exhibits a different crystal and electronic structure, which further affects the optical spectra because of the ligand effect. In combination with density functional theory (DFT) calculations, the differences in the UV/Vis spectra were found to be caused by the distinct electronic components of the frontier orbitals. In addition, accompanied by many recrystallization steps on Au15Ag3(SPhMe2)14, mass spectrometry analysis revealed that the by-products (i.e. Au14Ag4 and Ag13Ag5 nanoclusters) gradually decompose, and finally only the Au15Ag3 nanocluster exists. Our findings offer an extended insight into the ligand-induced variation on a nanocluster level.