The recent discovery on the total structure of Au36(SR)24, which was converted from biicosahedral Au38(SR)24, represents a surprising finding of a face-centered cubic (FCC)-like core structure in small gold-thiolate nanoclusters. Prior to this finding, the FCC feature was only expected for larger (nano)crystalline gold. Herein, we report results on the unique bonding properties of Au36(SR)24 that are associated with its FCC-like core structure. Temperature-dependent X-ray absorption spectroscopy (XAS) measurements at the Au L3-edge, in association with ab initio calculations, show that the local structure and electronic behavior of Au36(SR)24 are of more molecule-like nature, whereas its icosahedral counterparts such as Au38(SR)24 and Au25(SR)18 are more metal-like. Moreover, site-specific S K-edge XAS studies indicate that the bridging motif for Au36(SR)24 has different bonding behavior from the staple motif from Au38(SR)24. Our findings highlight the important role of "pseudo"-Au4 units within the FCC-like Au28 core in interpreting the bonding properties of Au36(SR)24 and suggest that FCC-like structure in gold thiolate nanoclusters should be treated differently from its bulk counterpart.
Keywords: XAFS; electronic behavior; face-centered-cubic geometry; gold−thiolate nanoclusters; local structure.