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

Abstract 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 synthesis isolation such defective NCs. Herein we report mixed‐ligand strategy synthesizing an intrinsically chiral metal‐deficient copper hydride‐rich NC [Cu 57 H 20 (PET) 36 (TPP) 4 ] + ( Cu ). Its total structure (including hydrides) electronic well established by combined experimental computational results. Crystal reveals features cube‐like 8 kernel embedded corner‐missing metal‐ligand shell 49 . Single site occurs at one corner shell, evocative mono‐lacunary polyoxometalates. Theoretical calculations demonstrate that above‐mentioned point causes hydride exposed as interfacial capping μ 3 ‐H − , which is accessible chemical reaction, proved deuterated experiment. Moreover, shows catalytic activity hydrogenation nitroarene. The success this work opens way for research well‐defined other metal NCs, including exploring their application asymmetrical catalysis.