Correlating the crystal structure of A thiol-protected Au25 cluster and optical properties

被引：0
|
作者：
Zhu, Manzhou [1 ]
Aikens, Christine M. [2 ]
Hollander, Frederick J. [3 ]
Schatz, George C. [4 ]
Jin, Rongchao [1 ]
机构：
[1] Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA 15213, United States
[2] Department of Chemistry, Kansas State University, Manhattan, KS 66506, United States
[3] College of Chemistry, University of California at Berkeley, Berkeley, CA 94720, United States
[4] Department of Chemistry, Northwestern University, Evanston, IL 60208, United States
来源：
Journal of the American Chemical Society | 2008年 / 130卷 / 18期
关键词：
The total structure determination of thiol-protected Au clusters has long been a major issue in cluster research. Herein; we report an unusual single crystal structure of a 25-gold-atom cluster (1.27 nm diameter; surface-to-surface distance) protected by eighteen phenylethanethiol ligands. The Au25 cluster features a centered icosahedral Au13 core capped by twelve gold atoms that are situated in six pairs around the three mutually perpendicular 2-fold axes of the icosahedron. The thiolate ligands bind to the Au25 core in an exclusive bridging mode. This highly symmetric structure is distinctly different from recent predictions of density functional theory; and it also violates the empirical golden rulecluster of clusters; which would predict a biicosahedral structure via vertex sharing of two icosahedral M13 building blocks as previously established in various 25-atom metal clusters protected by phosphine ligands. These results point to the importance of the ligand-gold core interactions. The Au25(SR)18 clusters exhibit multiple molecular-like absorption bands; and we find the results are in good correspondence with time-dependent density functional theory calculations for the observed structure. Copyright © 2008 American Chemical Society;
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页码：5883 / 5885
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