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High‐yield and large‐scale synthesis are highly demanded for the studies of gold nanoclusters. We developed a "cluster from cluster" approach to assemble gold nanoclusters with preformed atomically precise Au13 precursors. This facile approach has proved to be very effective in the synthesis of the well‐known magic cluster [Au25(SR)18]−, which could prepare the target cluster in high yield (overall yield up to ≈100 %) at large scale (gram‐scale based on gold). This method can be applied in the synthesis of 10 Au25 clusters with different R groups. This work presents an important approach that may be extended to high‐yield and large‐scale synthesis of other metal nanoclusters. [ABSTRACT FROM AUTHOR]

High‐yield and large‐scale synthesis are highly demanded for the studies of gold nanoclusters. We developed a "cluster from cluster" approach to assemble gold nanoclusters with preformed atomically precise Au13 precursors. This facile approach has proved to be very effective in the synthesis of the well‐known magic cluster [Au25(SR)18]−, which could prepare the target cluster in high yield (overall yield up to ≈100 %) at large scale (gram‐scale based on gold). This method can be applied in the synthesis of 10 Au25 clusters with different R groups. This work presents an important approach that may be extended to high‐yield and large‐scale synthesis of other metal nanoclusters. [ABSTRACT FROM AUTHOR]

Gold nanoclusters with surface open sites are crucial for practical applications in catalysis. We have developed a surface geometric mismatch strategy by using mixed ligands of different type of hindrance. When bulky phosphine Ph3P and planar dipyridyl amine (Hdpa) are simultaneously used, steric repulsion between the ligands will reduce the ligand coverage of gold clusters. A well‐defined access granted gold nanocluster [Au23(Ph3P)10(dpa)2Cl](SO3CF3)2 (Au23, dpa=dipyridylamido) has been successfully synthesized. Single crystal structural determination reveals that Au23 has eight uncoordinated gold atoms in the shape of a distorted bicapped triangular prism. The accessibility of the exposed Au atoms has been confirmed quantitatively by luminescent titration with 2‐naphthalenethiol. This cluster has excellent performance toward selective oxidation of benzyl alcohol to benzaldehyde and demonstrates excellent stability due to the protection of negatively charged multidentate ligand dpa. [ABSTRACT FROM AUTHOR]