Surface modifications of eight-electron palladium silver superatomic alloys

Atomically precise thiolate-protected coinage metal nanoclusters and their alloys are far more numerous than their selenium congeners, the synthesis of which remains extremely challenging. Herein, we report the synthesis of a series of atomically defined dithiophosph(in)ate protected eight-electron superatomic palladium silver nanoalloys [PdAg₂₀{S₂PR₂}₁₂], 2a-c (where R = OⁱPr, a; OⁱBu, b; Ph, c) via ligand exchange and/or co-reduction methods. The ligand exchange reaction on [PdAg₂₀{S₂P(OⁿPr)₂}₁₂], 1, with [NH₄{Se₂PR₂}₁₂] (where R = OⁱPr, or OⁿPr) leads to the formation of [PdAg₂₀{Se₂P(OⁱPr)₂}₁₂] (3) and [PdAg₂₀{Se₂P(OⁿPr)₂}₁₂] (4), respectively. Solid state structures of 2a, 2b, 3 and 4 unravel different PdAg₂₀ metal frameworks from their parent cluster, originating from the different distributions of the eight-capping silver(I) atoms around a Pd@Ag₁₂ centered icosahedron with C_2, D_3, T_h and T_h symmetries, respectively. Surprisingly ambient temperature crystallization of the reaction product 3 obtained by the ligand exchange reaction on 1 has resulted in the co-crystallization of two isomers in the unit cell with overall T (3a) and C₃ (3b) symmetries, respectively. To our knowledge, this is the first ever characterized isomeric pair among the selenolate-protected NCs. Density functional theory (DFT) studies further rationalize the preferred geometrical isomerism of the PdAg₂₀ core.