LAUSR

Silver nanoclusters have received unprecedented attention in cluster science owing to their promising functionalities and intriguing physical/chemical properties. However, essential instability significantly impedes their extensive applications. We herein propose a strategy termed “surface environment complication” to endow Ag29 nanoclusters with high robustness. The Ag29(S-Adm)18(PPh3)4 nanocluster with monodentate PPh3 ligands was extremely unstable and uncrystallizable. By substituting PPh3 with bidentate PPh2py with dual coordination sites (i.e., P and N), the Ag29 cluster framework was twisted because of the generation of N–Ag interactions, and three NO3 ligands were further anchored onto the nanocluster surface, yielding a new Ag29(S-Adm)15(NO3)3(PPh2py)4 nanocluster with high stability. The metal-control or ligand-control effects on stabilizing the Ag29 nanocluster were further evaluated. Besides, Ag29(S-Adm)15(NO3)3(PPh2py)4 followed a unique packing mode in the supracrystal lattice with several intercluster channels, which has yet been observed in other M29 cluster crystals. Overall, this work presents a new approach (i.e., surface environment complication) for tailoring the surface environment and improving the stability of metal nanoclusters.