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 structureproperty relationships. Herein, three well-characterized copper-hydride nanoclusters that provide insight into the surf...
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Veröffentlicht in: | Chemical science (Cambridge) 2022-12, Vol.13 (48), p.14357-14365 |
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Sprache: | eng |
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Zusammenfassung: | 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 structureproperty 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+
(
Cu
28
-PPh
2
Py
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
-C
6
H
11
)
18
(P(Ph-
p
Me)
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
-PPh
2
Py
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
-PPh
2
Py
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
-PPh
2
Py
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.
Structural adjustments in moving from surface-vacancy-defect
Cu
28
-PPh
2
Py
to non-defect
Cu
29
-P(Ph-Cl)
3
and
Cu
29
-P(Ph-Me)
3
provide valuable insight into the structures of surface vacancies in copper nanoclusters and structure-property relationships. |
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ISSN: | 2041-6520 2041-6539 |
DOI: | 10.1039/d2sc03239b |