Mechanistic insights into the two-phase synthesis of heteroleptic Au nanoclusters.

A mechanistic study on the two-phase synthesis of heteroleptic Au nanoclusters (NCs) is reported here. First, the effects of binary ligands on controlling the size of Au NCs were examined: (1) the binary ligands could exhibit an eclectic effect on the size control of Au NCs if the binding affinities of such hetero-ligands with Au are comparable and (2) the binary ligands could exhibit a competitive effect on the size control of Au NCs, and the size of the Au NCs could be determined by the ligand with stronger binding affinity to Au. This finding is interesting and can shed some light on the design of new functional metal NCs. Secondly, the formation mechanism of the heteroleptic Au NCs that originated from the complex precursors was unprecedentedly studied. The complex precursors of the heteroleptic Au NCs were identified to be the predominant hybridized ligand#1-Au(i)-ligand#2 species, which is helpful for understanding the synthetic mechanisms in depth. Moreover, the growth processes of the heteroleptic Au NCs were also monitored, and some fundamental perceptions about the growth pathway and the structures of the Au NCs were obtained.