[Pt₂Cu₃₄(PET)₂₂Cl₄]^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, [Pt₂Cu₃₄(PET)₂₂Cl₄]^2- NC, the first example of a Pt-doped Cu NC, is synthesized by utilizing the unique reactivity of [Cu₃₂(PET)₂₄Cl₂H₈]^2- NC with Pt⁴⁺ 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 (Pt₂Cu₁₈), which is stabilized by a Cu₁₆(PET)₂₂Cl₄ shell. The molecular structure and composition of the NC are validated by combined experimental and theoretical results. Electronic structure calculations, using the density functional theory, show that the Pt₂Cu₃₄ NC is a 10-electron superatom. The computed absorption spectrum matches well with the measured data and allows for assignment of the absorption peaks. The calculations also rationalize energetics for ligand exchange observed in the mass spectrometry data. The synergistic effects induced by Pt doping are found to enhance the catalytic activity of Cu NCs by ∼300-fold in silane to silanol conversion under mild conditions. Furthermore, our synthetic strategy has potential to produce Ni-, Pd-, and Au-doped Cu NCs, which will open new avenues to uncover their molecular structures and catalytic properties.