Reconstituting C-Centered Hexagold(I) Clusters with <i>N</i>-Heterocyclic Carbene Ligands

• Zhen Lei

  Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 , Japan

• Xiao-Li Pei

  Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 , Japan

• Hitoshi Ube

  Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 , Japan

• Mitsuhiko Shionoya

  Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 , Japan

Abstract

Ubiquitous intramolecular aurophilic interactions in gold clusters have usually been assigned as the main determinants of their molecular geometry and various properties. By utilizing N-heterocyclic carbene (NHC) ligands instead of phosphine ligands which have been exclusively used, we have developed ligand-specific photophysical properties of C-centered hexagold(I) (C@Au6) clusters. This account describes the recent development of carbene-protected C@Au6 clusters. First of all, a strong intramolecular C–H⋯Au interaction was found as a key structural feature of these clusters. These are also present in the newly emerged NHC-gold nanoclusters, but are negligible in the phosphine counterparts. Interestingly, the use of NHC ligands also produces clusters with a nearly identical metal kernel, but their luminescence changes significantly. In addition, a simple extension of the π-conjugated system of NHCs from imidazolylidene to benzimidazolylidene is expected to produce significant changes in both absorption coefficient and emission wavelength. These results show the promising potential of carbene ligands in character modulation of metal clusters, and may help in the rational design of carbene ligands for constructing functional metal clusters.

Journal

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 94 (4), 1324-1330, 2021-03-09

  Oxford University Press (OUP)

Keywords

• General Chemistry

Details

• CRID: 1360006529434595584
• NII Article ID: 130008037352
• DOI: 10.1246/bcsj.20210060
• ISSN: 13480634
• ISSN: 00092673
• Web Site: https://academic.oup.com/bcsj/article-pdf/94/4/1324/56311179/bcsj.20210060.pdf
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