Isomer Structural Transformation in Au–Cu Alloy Nanoclusters: Water Ripple‐Like Transfer of Thiol Ligands

Abstract Structure isomerism is observed in noble metal nanoclusters; however, the mechanism study of this process is rarely reported. Herein, by using the biphosphine ligands instead of phosphine ligands, the high symmetry of the Au 2 Cu 6 (PPh 3 ) 2 (SAdm) 6 nanocluster is successfully broken and [Au 4 Cu 4 (L 1 ) 2 (SAdm) 5 ]Br (where, L 1 is bis(diphenylphosphine)methane, DPPM) nanocluster is obtained with chiral arrangement. This newly obtained nanocluster contains a total of four isomers in crystal unit cell. Interestingly, these isomers undergo rapid isomorphism in solution, which is confirmed by 1 H‐ 1 H COSY spectrum. Density functional theory calculations demonstrate that the water ripple–like transfer of the thiol ligands results from the isomorphism of nanoclusters.