Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2019 Feb 4;10(11):3360-3365.
doi: 10.1039/c8sc03756f. eCollection 2019 Mar 21.

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

Zong-Jie Guan  1   2 , Feng Hu  2 , Shang-Fu Yuan  1   2 , Zi-Ang Nan  1 , Yu-Mei Lin  1 , Quan-Ming Wang  1   2
Affiliations

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

Zong-Jie Guan et al. Chem Sci. .

Abstract

We report the synthesis and structures of two 34-atom metal nanoclusters, namely [Ag34(BTCA)3(C[triple bond, length as m-dash]CBu t )9(tfa)4(CH3OH)3]SbF6 and [AuAg33(BTCA)3(C[triple bond, length as m-dash]CBu t )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 t BuC[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.

PubMed Disclaimer

Figures

Scheme 1
Scheme 1. Two types of coordination motifs: (a) Ag4@H2BTCA and (b) Ag5@BTCA.
Fig. 1
Fig. 1. (a) Molecular structure of 1. (b) Ag34 kernel in 1. (c) The additional 12 Ag atoms (sky blue) held by thiacalixarene ligands onto the Ag@Ag12 core (green). (d) The 9 peripheral Ag atoms (sky blue) coordinated by alkynyl, tfa and MeOH ligands. Color legend: green, sky blue, silver; red, oxygen; yellow, sulfur; gray, carbon; bright green, fluorine. Hydrogen atoms were omitted for clarity.
Fig. 2
Fig. 2. (a) Mass spectrum of cluster 1. (b) The measured (blue trace) and simulated (red trace) isotopic patterns of [Ag34(BTCA)3(CCBut)9(tfa)2Cl]2+ (I) and [Ag34(BTCA)3(CCBut)9(tfa)3]2+ (II).
Fig. 3
Fig. 3. (a) Molecular structure of 2. (b) Metal core AuAg33 in 2. Color legend: green, silver; red, oxygen; yellow, sulfur; gray, carbon; bright green, fluorine. Hydrogen atoms were omitted for clarity.
Fig. 4
Fig. 4. The optical absorption spectra of [Ag34(BTCA)3(CCBut)9(tfa)4(CH3OH)3](SbF6) (1) and [AuAg33(BTCA)3(CCBut)9(tfa)4(CH3OH)3](SbF6) (2) in dichloromethane solution. Inset: photographs of cluster solutions.
Fig. 5
Fig. 5. (a) Time dependences of absorption spectra of 1 in CH2Cl2. (b) Time dependences of absorption spectra of 2 in CH2Cl2. (c) Time dependences of absorption spectra of Ag35 in CH2Cl2.
See this image and copyright information in PMC

Similar articles

See all similar articles

Cited by

See all "Cited by" articles

References

    1. Daniel M. C., Astruc D. Chem. Rev. 2004;104:293–346. - PubMed
    1. Jin R., Zeng C., Zhou M., Chen Y. Chem. Rev. 2016;116:10346–10413. - PubMed
    1. Parker J. F., Fields-Zinna C. A., Murray R. W. Acc. Chem. Res. 2010;43:1289–1296. - PubMed
    1. Schmid G. Chem. Soc. Rev. 2008;37:1909–1930. - PubMed
    1. Jin R. X., Zhao S., Xing Y., Jin R. CrystEngComm. 2016;18:3996–4005.