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Abstract
With the recent successful synthesis of an increasing number of atomically precise thiolate–gold nanoclusters (NCs), there are growing demands for a better understanding of their atomic structures and structure–property relationships in response to composition change. Herein, we present X-ray experimental results on structural and electronic properties of a recently synthesized gold–thiolate nanocluster, Au19(SR)13, in comparison with the structurally well-known Au25(SR)18 reference. The atomic structure of Au19(SR)13 was first probed with extended X-ray absorption fine structure (EXAFS). A multishell EXAFS fitting method (consisting of one Au–S and three Au–Au shells) allowed for a detailed structural comparison of the two nanoclusters, which revealed a sizable increase of the bond distances between the surface–surface and surface–staple Au atoms upon the decrease of Au atoms in the nanocluster. X-ray photoemission experiments and ab initio calculations further demonstrated the sensitive change of electr...
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