Despite substantial progress in ligand engineering, the efforts in the field of Au nanoclusters have been concentrated almost exclusively on organic ligands. Halides, the most typical auxiliary inorganic ligands widely present in Au clusters, remain virtually unexplored, particularly regarding their effects on cluster construction. Herein, diphosphine PhP(CH)PPh (L, n = 1-6) is chosen as the co-protecting organic ligands and a comparative analysis on the influential roles of halide ions (Cl, Br, I) in guiding Au cluster synthesis is conducted.
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