Atom-by-Atom Evolution of the Same Ligand-Protected Au21, Au22, Au22Cd1, and Au24Nanocluster Series

Yingwei Li, Michael J. Cowan, Meng Zhou, Tian Yi Luo, Yongbo Song, He Wang, Nathaniel L. Rosi, Giannis Mpourmpakis, Rongchao Jin

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

Atom-by-atom manipulation on metal nanoclusters (NCs) has long been desired, as the resulting series of NCs can provide insightful understanding of how a single atom affects the structure and properties as well as the evolution with size. Here, we report crystallizations of Au22(SAdm)16 and Au22Cd1(SAdm)16 (SAdm = adamantanethiolate) which link up with Au21(SAdm)15 and Au24(SAdm)16 NCs and form an atom-by-atom evolving series protected by the same ligand. Structurally, Au22(SAdm)16 has an Au3(SAdm)4 surface motif which is longer than the Au2(SAdm)3 on Au21(SAdm)15, whereas Au22Cd1(SAdm)16 lacks one staple Au atom compared to Au24(SAdm)16 and thus the surface structure is reconstructed. A single Cd atom triggers the structural transition from Au22 with a 10-atom bioctahedral kernel to Au22Cd1 with a 13-atom cuboctahedral kernel, and correspondingly, the optical properties are dramatically changed. The photoexcited carrier lifetime demonstrates that the optical properties and excited state relaxation are highly sensitive at the single atom level. By contrast, little change in both ionization potential and electron affinity is found in this series of NCs by theoretical calculations, indicating the electronic properties are independent of adding a single atom in this series. The work provides a paradigm that the NCs with continuous metal atom numbers are accessible and crystallizable when meticulously designed, and the optical properties are more affected at the single atom level than the electronic properties.

Original languageEnglish (US)
Pages (from-to)20426-20433
Number of pages8
JournalJournal of the American Chemical Society
Volume142
Issue number48
DOIs
StatePublished - Dec 2 2020
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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