Surface environment complication makes Ag₂₉ nanoclusters more robust and leads to their unique packing in the...

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.