Structural Design of Thiolate‐Protected Gold Nanoclusters

In 2007, the breakthrough in the X-ray structure determination of Au 102 ( p -MBA) 44 ( p -MBA = p -mercaptobenzoic acid) nanocluster, which comprises 102 gold atoms and 44 p-MBAs, greatly promoted the theoretical exploration of new methods to understand and design the atomic structures of thiolate-protected gold nanoclusters. A new ligand-binding strategy for predicting the structures of thiolate-protected gold nanoclusters has been developed via redistribution of the Au–S “staple” motifs on the well-determined Au core structures. A Grand Unified Model (GUM) is developed to achieve fundamental understanding of the rich and complex structures of all the 71 ligand-protected gold clusters reported up to date. The composite particles in the GUM are categorized into two groups: the triangular elementary block Au 3 and the tetrahedral elementary block Au 4 . This chapter presents four methods for designing the atomic structures of thiolate-protected gold nanoclusters. It provides some future perspectives on the structural design of nanoclusters.