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This work presents a controlled reduction method for the selective synthesis of different sized gold nanoclusters protected by thiolate (SR = SC 2 H 4 Ph). Starting with Au(III) salt, all the syntheses of Au  n  (SR)  m   nanoclusters with ( n ,  m ) = (20, 16), (24, 20), (39, 29), and (40, 30) necessitate experimental conditions of slow stirring and slow reduction of Au(I) intermediate species. By controlling the reaction kinetics for the reduction of Au(I) into clusters by NaBH 4 , different sized gold nanoclusters are selectively obtained. Two factors are identified to be important for the selective growth of Au 20 , Au 24 , and Au 39/40  nanoclusters, including the stirring speed of the Au(I) solution and the NaBH 4  addition speed during the step of Au(I) reduction to clusters. When comparing with the synthesis of Au 25 (SC 2 H 4 Ph) 18  nanoclusters, we further identified that the reduction degree of Au(I) by NaBH 4  also plays an important role in controlling cluster size. Overall, our results demonstrate the feasibility of attaining new sizes of gold nanoclusters via a controlled reduction route.

Controlled reduction for size selective synthesis of thiolate-protected gold nanoclusters Aun(n = 20, 24, 39, 40)