Rare-Earth-Driven In Situ Core Evolution: Divergent Assembly of Octamolybdate- and Silverton-Type Templated Silver Nanoclusters

Polyoxometalate (POM) anions serve as templates for constructing high-nuclearity silver nanoclusters. Utilizing rare-earth-containing POMs, particularly metastable Silverton-type architectures, remains a synthetic challenge. Herein, a rare-earth-driven in situ core evolution strategy is reported for the construction of a high-nuclearity silver cluster. By introducing dysprosium nitrate, the assembly pathway was redirected from the octamolybdate-templated [Mo 8 O 28 @Ag 48 (CyhS) 24 (CF 3 COO) 16 (CH 3 CN) 4 ]·5DMF ( Mo 8 @Ag 48, CyhS = cyclohexanethiolate) baseline to yield a Silverton-templated [DyMo 12 O 42 @Ag 54 (CyhS) 30 (CF 3 COO) 6 ]·9NO 3 ·4CH 2 Cl 2 ·4DMF ( DyMo 12 @Ag 54 ) cluster. Structural analysis reveals that DyMo 12 @Ag 54 features a pseudoicosahedral Silverton-type [DyMo 12 O 42 ] 9– core. The incorporation of this lanthanide-containing core expands the outer silver shell from 48 to 54 atoms. This “core-swelling” effect and the interaction between the core and shell result in a narrowed optical bandgap, a 3.5-fold increase in photocurrent response, and accelerated photocatalytic degradation kinetics compared to Mo 8 @Ag 48, alongside a red-shift in near-infrared photoluminescence. This work expands the variety of POM templates and demonstrates a strategy for tailoring the properties of silver nanoclusters via inner-template engineering.