Development of Stable Water‐Soluble Supratomic Silver Clusters Utilizing A Polyoxoniobate‐Protected Strategy: Giant Core‐Shell‐Type Ag<sub>8</sub>@Nb<sub>162</sub> Fluorescent Nanocluster
Li‐Hao Hong, Shengnan Yue, Xing Huang, Cai Sun, Pingwei Cai, Yan‐Qiong Sun, Xin‐Xiong Li, Shou‐Tian Zheng
Abstract
Abstract Atomically precise low‐nuclearity ( n <10) silver nanoclusters (AgNCs) have garnered significant interest due to their size‐dependent optical properties and diverse applications. However, their synthesis has remained challenging, primarily due to their inherent instability. The present study introduces a new feasible approach for clustering silver ions utilizing highly negative and redox‐inert polyoxoniobates (PONbs) as all‐inorganic ligands. This strategy not only enables the creation of novel Ag‐PONb composite nanoclusters but also facilitates the synthesis of stable low‐nuclearity AgNCs. Using this method, we have successfully synthesized a small octanuclear rhombic [Ag 8 ] 6+ AgNC stabilized by six highly negative [LiNb 27 O 75 ] 14− polyoxoanions. This marks the first PONb‐protected superatomic AgNC, designated as {Ag 8 @(LiNb 27 O 75 ) 6 } ( Ag 8 @Nb 162 ), with an aesthetically spherical core–shell structure. The crystalline Ag 8 @Nb 162 is stable under ambient conditions, What's more, it is water‐soluble and able to maintain its molecular cluster structure intact in water. Further, the stable small [Ag 8 ] 6+ AgNC has interesting temperature‐ and pH‐dependent reversible fluorescence response, based on which a multiple optical encryption mode for anti‐counterfeit technology was demonstrated. This work offers a promising avenue for the synthesis of fascinating and stable PONb‐protected AgNCs and sheds light on the development of new‐type optical functional materials.