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 [Mo8O28@Ag48(CyhS)24(CF3COO)16(CH3CN)4]·5DMF (Mo8@Ag48, CyhS = cyclohexanethiolate) baseline to yield a Silverton-templated [DyMo12O42@Ag54(CyhS)30(CF3COO)6]·9NO3·4CH2Cl2·4DMF (DyMo12@Ag54) cluster. Structural analysis reveals that DyMo12@Ag54 features a pseudoicosahedral Silverton-type [DyMo12O42]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 Mo8@Ag48, 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.