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 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.