Total Structure, Electronic Structure and Catalytic Hydrogenation Activity of Metal‐Deficient Chiral Polyhydride Cu₅₇ Nanoclusters

Accurate identifying and in-depth understanding of the defect sites in a working nanomaterial could hinge on establishing specific defect-activity relationships. Yet, atomically precise coinage-metal nanoclusters (NCs) possessing surface vacancy defects are scarce primarily owing to challenges in the synthesis and isolation of such defective NCs. Herein we report a mixed-ligand strategy to synthesizing an intrinsically chiral and metal-deficient copper hydride-rich NC [Cu₅₇ H₂₀ (PET)₃₆ (TPP)₄ ]⁺ (Cu₅₇ H₂₀ ). Its total structure (including hydrides) and electronic structure are well established by combined experimental and computational results. Crystal structure reveals Cu₅₇ H₂₀ features a cube-like Cu₈ kernel embedded in a corner-missing metal-ligand shell of Cu₄₉ (PET)₃₆ (TPP)₄ . Single Cu vacancy defect site occurs at one corner of the shell, evocative of mono-lacunary polyoxometalates. Theoretical calculations demonstrate that the above-mentioned point vacancy causes one surface hydride exposed as an interfacial capping μ₃ -H⁻ , which is accessible in chemical reaction, as proved by deuterated experiment. Moreover, Cu₅₇ H₂₀ shows catalytic activity in the hydrogenation of nitroarene. The success of this work opens the way for the research on well-defined chiral metal-deficient Cu and other metal NCs, including exploring their application in asymmetrical catalysis.