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Updated: Jun 15, 2025

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Published on: March 2, 2016
All-Calixarene-Protected Silver Nanocluster with All Silver Atoms in a Face-Centered Cubic Arrangement
Lu-Ming Zheng1, Wan-Qi Shi1, Feng Hu1
1Department of Chemistry, Engineering Research Center of Advanced Rare Earth Materials (Ministry of Education), Tsinghua University, Beijing 100084, P. R. China.
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] (Ag, 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 Ag due to its multiple coordination sites and bulkiness. Mass spectrometry and theoretical calculations reveal that Ag 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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