The photoelectron spectra of Au2Sin− (n = 1–7) clusters were measured, and the structural evolution and bonding properties of Au2Si1–7− anions and their corresponding neutral counterparts were investigated by theoretical calculations. The two Au atoms in Au2Si1–7−/0 prefer to occupy low coordinate sites and form fewer Au–Si bonds. The aurophilic interaction is fairly weak in these clusters. The most stable structures of both Au2Sin− anions and Au2Sin neutrals can be described as the two Au atoms interacting with the Sin frameworks. The most stable isomers of Au2Sin− anions are in spin doublet states, while those of the neutral clusters are in spin singlet states. The lowest-lying isomers of Au2Si1−/0 have C2v symmetric V-shaped structures. The global minimum of the Au2Si2− anion has a D2h symmetric planar rhombus structure, while that of the Au2Si2 neutral adopts a C2v symmetric dibridged structure. In Au2Si3−/0, the two Au atoms independently interact with the different Si–Si bonds of the Si3 triangular structure. The global minima of Au2Si4–7−/0 primarily adopt prismatic based geometries. Interestingly, Au2Si6−/0 have significant 3D aromaticity and possess σ plus π double bonding characters, which play important roles in their structural stability.
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