This work was financially supported by the Ministry of Education, Singapore, under Grants R-279-000-409-112, R-279-000-383-112, and R-279-000-387-112. X.Y., B.Z., Z.L., and Q.Y. acknowledge the NUS for their research scholarships.
Balancing the Rate of Cluster Growth and Etching for Gram-Scale Synthesis of Thiolate-Protected Au25 Nanoclusters with Atomic Precision†
Article first published online: 24 MAR 2014
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Angewandte Chemie International Edition
Volume 53, Issue 18, pages 4623–4627, April 25, 2014
How to Cite
Yuan, X., Zhang, B., Luo, Z., Yao, Q., Leong, D. T., Yan, N. and Xie, J. (2014), Balancing the Rate of Cluster Growth and Etching for Gram-Scale Synthesis of Thiolate-Protected Au25 Nanoclusters with Atomic Precision. Angew. Chem. Int. Ed., 53: 4623–4627. doi: 10.1002/anie.201311177
- Issue published online: 25 APR 2014
- Article first published online: 24 MAR 2014
- Manuscript Received: 24 DEC 2013
- Ministry of Education, Singapore. Grant Numbers: R-279-000-409-112, R-279-000-383-112, R-279-000-387-112
- noble metal clusters;
- surface chemistry;
- synthesis (inorg.);
We report a NaOH-mediated NaBH4 reduction method for the synthesis of mono-, bi-, and tri-thiolate-protected Au25 nanoclusters (NCs) with precise control of both the Au core and thiolate ligand surface. The key strategy is to use NaOH to tune the formation kinetics of Au NCs, i.e., reduce the reduction ability of NaBH4 and accelerate the etching ability of free thiolate ligands, leading to a well-balanced reversible reaction for rapid formation of thermodynamically favorable Au25 NCs. This protocol is facile, rapid (≤3 h), versatile (applicable for various thiolate ligands), and highly scalable (>1 g Au NCs). In addition, bi- and tri-thiolate-protected Au25 NCs with adjustable ratios of hetero-thiolate ligands were easily obtained. Such ligand precision in molecular ratios, spatial distribution and uniformity resulted in richly diverse surface landscapes on the Au NCs consisting of multiple functional groups such as carboxyl, amine, and hydroxy. Analysis based on NMR spectroscopy revealed that the hetero-ligands on the NCs are well distributed with no ligand segregation. The unprecedented synthesis of multi-thiolate-protected Au25 NCs may further promote the practical applications of functional metal NCs.