Issue 11, 2019

The stability enhancement factor beyond eight-electron shell closure in thiacalix[4]arene-protected silver clusters

Abstract

We report the synthesis and structures of two 34-atom metal nanoclusters, namely [Ag34(BTCA)3(C[triple bond, length as m-dash]CBut)9(tfa)4(CH3OH)3]SbF6 and [AuAg33(BTCA)3(C[triple bond, length as m-dash]CBut)9(tfa)4(CH3OH)3]SbF6, where H4BTCA is p-tert-butylthiacalix[4]arene and tfa is trifluoroacetate. Their compositions and structures have been determined by single-crystal X-ray structural analysis and ESI-MS. The cationic cluster consists of a centered icosahedron M@Ag12 (M = Ag or Au) core that is surrounded by 21 peripheral silver atoms. Surrounding protection is provided by four kinds of ligands, including three BTCA, nine tBuC[triple bond, length as m-dash]C, four tfa, and three methanol solvent ligands. It was found that the Ag5@BTCA μ5-coordination motif of thiacalixarene is critical for high stability of the title clusters, and extra stability enhancement can be achieved by doping a gold atom at the center of the silver cluster. This work suggests that coordination saturation should be taken into account in addition to electronic and geometric factors for analyzing metal nanocluster stabilities.

Graphical abstract: The stability enhancement factor beyond eight-electron shell closure in thiacalix[4]arene-protected silver clusters

Supplementary files

Article information

Article type
Edge Article
Submitted
22 aug 2018
Accepted
02 feb 2019
First published
04 feb 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2019,10, 3360-3365

The stability enhancement factor beyond eight-electron shell closure in thiacalix[4]arene-protected silver clusters

Z. Guan, F. Hu, S. Yuan, Z. Nan, Y. Lin and Q. Wang, Chem. Sci., 2019, 10, 3360 DOI: 10.1039/C8SC03756F

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