Unusual fcc-structured Ag₁₀ kernels trapped in Ag₇₀ nanoclusters

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Abstract

Controlled trapping atom-precise ultrasmall silver nanoparticles into silver nanoclusters is challenging; thus only limited progress has been made in this area. We are therefore inspired to isolate two novel silver nanoclusters, Ag₁₀@Ag₇₀ (SD/Ag80a and SD/Ag80b; SD = SunDi), where a novel fcc-structured Ag₁₀ kernel built from two single-edge opened Ag₆ octahedra by sharing one edge is trapped. The bioctahedral Ag₁₀ kernel is locked by a pair of Mo₇O₂₆ 10- anions to form an inner Ag₁₀@(Mo₇O₂₆)₂ core which is further encapsulated by an outer Ag₇₀ shell to form three-shell Ag₁₀@(Mo₇O₂₆)₂@Ag₇₀ nanoclusters. Notably, the bioctahedral Ag₁₀ kernel has not been observed in silver nanoclusters ever before, thus representing a new embryo state of silver nanoparticles. SD/Ag80a emits in the near infrared (NIR) region (λ _em = 730 nm) at low temperature. This work will deepen our understanding on the atomic-level growth of silver nanoparticles and complicated three-shell self-assembly involving polyoxometalate (POM) and two different silver nanoclusters.

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