Identification of an eight-electron superatomic cluster and its alloy in one co-crystal structure

International audienceHerein we report a crystal structure of [Au0.5Ag0.5@Ag20{S2P(OiPr)2}12](PF6) [Cl@Ag8{S2P(OiPr)2}6](PF6) (1), which compositions were supported by positive-mode electrospray ionization mass spectrometry. The structural elucidation indicates that the encapsulated atom of an Ag13 the entered icosahedron can be replaced by a gold atom. Surprisingly, the capping Ag atoms on the surface of an icosahedron in 1 reveal a different arrangement from the previously reported [Ag21{S2P(OiPr)2}12](PF6) of C3 symmetry. Besides, the preference for the central silver atom being oxidized by Au(I) is rationalized by the DFT calculations on three different computed [AuAg20{S2PH2}12]+ models having C1, C3, and T symmetry, respectively