A Small Structural Change Makes a Big Difference: Synthesis of a Bowl‐Like Polyoxometalate‐Encapsulated {Ag ₇ } ⁵⁺ Cluster and Its Structural Derivatives

Ligand‐induced structural transformation has been developed as an effective strategy to manipulate the geometric/electronic structures, elemental compositions, and physicochemical properties of atomically precise silver clusters. In this work, we have demonstrated how a small structural change in the configuration of a bowl‐like antimonotungstate ( {Sb 3 W 30 }‐3 ) ligand can make a big difference in the synthesis of polyoxometalate (POM)‐encapsulated Ag clusters (Ag n @POM). The new bowl‐like {Sb 3 W 30 }‐3 can successfully induce the formation of a {Ag 7 } cluster, {Ag 7 (Sb 3 W 30 )} . Interestingly, the {Ag 7 (Sb 3 W 30 )} cluster, which can generate exposed Ag sites upon removal of three labile CH 3 CN ligands, serves as a common building block for constructing three new types of Ag n @POM derivatives, namely polymeric {Ag 7 (Sb 3 W 30 )} n , {Ag 15 (Sb 3 W 30 ) 2 } , and {Ag 23 (Sb 3 W 30 ) 2 } , via either inter‐cluster assembly or intra‐cluster kernel growth processes. In addition, photocatalytic H 2 evolution studies reveal the importance of accessibility to highly exposed Ag active sites and their synergistic cooperation with the redox‐active bowl‐like {Sb 3 W 30 }‐3 ligand. This study establishes a strategic platform for the rational design and structural evolution of Ag n @POM clusters, demonstrating how subtle modulation of all‐inorganic POM ligands influences their geometric and catalytic properties at the atomic level.