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

Abstract

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>i.e.</i>, 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>i.e.</i>, surface environment complication) for tailoring the surface environment and improving the stability of metal nanoclusters.