Surface environment complication makes Ag 29 nanoclusters more robust and leads to their unique packing in the supracrystal lattice.

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 Ag 29 nanoclusters with high robustness. The Ag 29 (S-Adm) 18 (PPh 3 ) 4 nanocluster with monodentate PPh 3 ligands was extremely unstable and uncrystallizable. By substituting PPh 3 with bidentate PPh 2 py with dual coordination sites ( i.e. , P and N), the Ag 29 cluster framework was twisted because of the generation of N-Ag interactions, and three NO 3 ligands were further anchored onto the nanocluster surface, yielding a new Ag 29 (S-Adm) 15 (NO 3 ) 3 (PPh 2 py) 4 nanocluster with high stability. The metal-control or ligand-control effects on stabilizing the Ag 29 nanocluster were further evaluated. Besides, Ag 29 (S-Adm) 15 (NO 3 ) 3 (PPh 2 py) 4 followed a unique packing mode in the supracrystal lattice with several intercluster channels, which has yet been observed in other M 29 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.