Structured copper-hydride nanoclusters provide insight into the surface-vacancy-defect to non-defect structural...

Exploring the structural evolution of clusters with similar sizes and atom numbers induced by the removal or addition of a few atoms contributes to a deep understanding of structure-property relationships. Herein, three well-characterized copper-hydride nanoclusters that provide insight into the surface-vacancy-defect to non-defect structural evolution were reported. A surface-defective copper hydride nanocluster [Cu₂₈(S-c-C₆H₁₁)₁₈(PPh₂Py)₃H₈]²⁺ (Cu₂₈-PPh₂Py for short) with only one C ₁ symmetry axis was synthesized using a one-pot method under mild conditions, and its structure was determined. Through ligand regulation, a 29^th copper atom was inserted into the surface vacancy site to give two non-defective copper hydride nanoclusters, namely [Cu₂₉(SAdm)₁₅Cl₃(P(Ph-Cl)₃)₄H₁₀]⁺ (Cu₂₉-P(Ph-Cl)₃ for short) with one C ₃ symmetry axis and (Cu₂₉(S-c-C₆H₁₁)₁₈(P(Ph-^pMe)₃)₄H₁₀)⁺ (Cu₂₉-P(Ph-Me)₃ for short) with four C ₃ symmetry axes. The optimized structures show that the 10 hydrides cap four triangular and all six square-planar structures of the cuboctahedral Cu₁₃ core of Cu₂₉-P(Ph-Me)₃, while the 10 hydrides cap four triangular and six square-planar structures of the anti-cuboctahedral Cu₁₃ core of Cu₂₉-P(Ph-Cl)₃, with the eight hydrides in Cu₂₈-PPh₂Py capping four triangular and four square planar-structures of its anti-cuboctahedral Cu₁₃ core. Cluster stability was found to increase sequentially from Cu₂₈-PPh₂Py to Cu₂₉-P(Ph-Cl)₃ and then to Cu₂₉-P(Ph-Me)₃, which indicates that stability is affected by the overall structure of the cluster. Structural adjustments to the metal core, shell, and core-shell bonding model, in moving from Cu₂₈-PPh₂Py to Cu₂₉-P(Ph-Cl)₃ and then to Cu₂₉-P(Ph-Me)₃, enable the structural evolution and mechanism responsible for their physicochemical properties to be understood and provide valuable insight into the structures of surface vacancies in copper nanoclusters and structure-property relationships.