In:
Chemical Science, Royal Society of Chemistry (RSC), Vol. 13, No. 48 ( 2022), p. 14357-14365
Abstract:
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 -C 6 H 11 ) 18 (PPh 2 Py) 3 H 8 ] 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 [Cu 29 (SAdm) 15 Cl 3 (P(Ph-Cl) 3 ) 4 H 10 ] + (Cu29-P(Ph-Cl)3 for short) with one C 3 symmetry axis and (Cu 29 (S- c -C 6 H 11 ) 18 (P(Ph- p Me) 3 ) 4 H 10 ) + (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 Cu 13 core of Cu29-P(Ph-Me)3, while the 10 hydrides cap four triangular and six square-planar structures of the anti-cuboctahedral Cu 13 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 Cu 13 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.
Type of Medium:
Online Resource
ISSN:
2041-6520
,
2041-6539
Language:
English
Publisher:
Royal Society of Chemistry (RSC)
Publication Date:
2022
detail.hit.zdb_id:
2559110-1
Bookmarklink
