All-Calixarene-Protected Silver Nanocluster with All Silver Atoms in a Face-Centered Cubic Arrangement.
J Am Chem Soc
; 146(36): 25101-25107, 2024 Sep 11.
Article
em En
| MEDLINE
| ID: mdl-39196903
ABSTRACT
Tailoring the surface ligands of metal nanoclusters is important for engineering unique configurations of metal nanoclusters. Thiacalix[4]arene has found extensive applications in the construction of metal nanoclusters. In this investigation, we present the synthesis and characterization of the first all-calixarene-protected silver nanoclusters, [Ag(CH3CN)4]2[Ag44(BTCA)6] (Ag44, H4BTCA = p-tert-butylthiacalix[4]arene). Single-crystal X-ray structural analysis reveals that all silver atoms are in a face-centered cubic (fcc) arrangement. The formation of such an fcc structure is attributed to the selectively passivation on {100} facets by BTCA4-. Thiacalixarene substantially facilitates the stability of Ag44 due to its multiple coordination sites and bulkiness. Mass spectrometry and theoretical calculations reveal that Ag44 is a superatomic silver nanocluster with 22 free electrons in the following configuration 1S21P61D61F22S21D4. This work not only elucidates the impact of macrocyclic ligands on the stabilization of silver clusters but also furnishes an approach for assembling atomically precise fcc nanoclusters.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Ano de publicação:
2024
Tipo de documento:
Article