The stability enhancement factor beyond eight-electron shell closure in thiacalix[4]arene-protected silver clusters† †Electronic supplementary information (ESI) available. CCDC 1863292 and 1863293. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8sc03756f
Destroying coordination open sites may significantly enhance the stability of metal nanoclusters. We report the synthesis and structures of two 34-atom metal nanoclusters, namely [Ag 34 (BTCA) 3 (C Created by potrace 1.16, written by Peter Selinger 2001-2019 CBu t ) 9 (tfa) 4 (CH 3 OH) 3 ]SbF 6 and...
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Published in | Chemical science (Cambridge) Vol. 10; no. 11; pp. 3360 - 3365 |
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Main Authors | , , , , , |
Format | Journal Article |
Language | English |
Published |
Royal Society of Chemistry
04.02.2019
|
Subjects | |
Online Access | Get full text |
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Summary: | Destroying coordination open sites may significantly enhance the stability of metal nanoclusters.
We report the synthesis and structures of two 34-atom metal nanoclusters, namely [Ag
34
(BTCA)
3
(C
Created by potrace 1.16, written by Peter Selinger 2001-2019
CBu
t
)
9
(tfa)
4
(CH
3
OH)
3
]SbF
6
and [AuAg
33
(BTCA)
3
(C
Created by potrace 1.16, written by Peter Selinger 2001-2019
CBu
t
)
9
(tfa)
4
(CH
3
OH)
3
]SbF
6
, where H
4
BTCA 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@Ag
12
(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
t
BuC
Created by potrace 1.16, written by Peter Selinger 2001-2019
C, four tfa, and three methanol solvent ligands. It was found that the Ag
5
@BTCA μ
5
-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. |
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ISSN: | 2041-6520 2041-6539 |
DOI: | 10.1039/c8sc03756f |