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

Jian-Hong Liao (1) , Samia Kahlal (2) , Yu-Chiao Liu (3) , Ming-Hsi Chiang (3) , Jean-Yves Saillard (2) , C.W. Liu (1)

1 NDHU - National Dong Hwa University
2 ISCR - Institut des Sciences Chimiques de Rennes
3 Institute of Chemistry

Herein 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.

Keywords: gold; superatoms; co-crystallization; silver; alloys

Domains: Chemical Sciences; Cristallography; Chemical Sciences; Inorganic chemistry

Jian-Hong Liao, Samia Kahlal, Yu-Chiao Liu, Ming-Hsi Chiang, Jean-Yves Saillard, et al.. Identification of an eight-electron superatomic cluster and its alloy in one co-crystal structure. Journal of Cluster Science, 2018, 29 (5), pp.827-835. ⟨10.1007/s10876-018-1353-y⟩. ⟨hal-01874569⟩