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

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 [Cu-28(S-c-C6H11)(18)(PPh2Py)(3)H-8](2+) (Cu-28-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 [Cu-29(SAdm)(15)Cl-3(P(Ph-Cl)(3))(4)H-10](+) (Cu-29-P(Ph-Cl)(3) for short) with one C-3 symmetry axis and (Cu-29(S-c-C6H11)(18)(P(Ph-Me-p)(3))(4)H-10)(+) (Cu-29-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 Cu-13 core of Cu-29-P(Ph-Me)(3), while the 10 hydrides cap four triangular and six square-planar structures of the anti-cuboctahedral Cu-13 core of Cu-29-P(Ph-Cl)(3), with the eight hydrides in Cu-28-PPh2Py capping four triangular and four square planar-structures of its anti-cuboctahedral Cu-13 core. Cluster stability was found to increase sequentially from Cu-28-PPh2Py to Cu-29-P(Ph-Cl)(3) and then to Cu-29-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 Cu-28-PPh2Py to Cu-29-P(Ph-Cl)(3) and then to Cu-29-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.

Automated summary

This article reports the structural evolution of three copper-hydride nanoclusters and investigates their surface vacancy defect to non-defect transformation. It was found that the stability of the clusters increases with structural adjustments. These findings are important for understanding the structure-property relationship of nanoclusters.