[Pt 2 Cu 34 (PET) 22 Cl 4 ] 2– : An Atomically Precise, 10-Electron PtCu Bimetal Nanocluster with a Direct Pt–Pt Bond

Heteroatom-doped metal nanoclusters (NCs) are highly desirable to gain fundamental insights into the effect of doping on the electronic structure and catalytic properties. Unfortunately, their controlled synthesis is highly challenging when the metal atomic sizes are largely different (e.g., Cu and Pt). Here, we design a metal-exchange strategy that enables simultaneous doping and resizing of NCs. Specifically, [Pt 2 Cu 34 (PET) 22 Cl 4 ] 2– NC, the first example of a Pt-doped Cu NC, is synthesized by utilizing the unique reactivity of [Cu 32 (PET) 24 Cl 2 H 8 ] 2– NC with Pt 4+ ions. The single-crystal X-ray structure reveals that two directly bonded Pt atoms occupy the two centers of an unusually interpenetrating, incomplete biicosahedron core (Pt 2 Cu 18 ), which is stabilized by a Cu 16 (PET) 22 Cl 4 shell. The molecular structure and composition of the NC are validated by combined e…