Polyoxometalates can be used as templates for the synthesis of high-nuclearity silver cluster systems.

Shuang-Qun Zang, Guang-Gang Hao, and colleagues at Zhengzhou University and Jiamusi University, both China, have come up with a core–shell cluster formed by self-assembly of metavanadate and silver(I) salts. The cluster comprises a C_2h dodecahedrane-like [Ag₃₀(^tBuS)₂₀]¹⁰⁺ unit that encapsulates a [V^V₁₀V^IV₂O₃₄]^10– core.

Upon acidification, the core transforms to a higher–symmetry D_3d configuration and the color of the complex changes from dark yellow to green. Further treatment with base leads to a core–shell species virtually identical to the starting compound. The structural transformation was studied by using single-crystal X–ray crystallography, which is rare for this type of system. This work provides new insights into the behavior and properties of core–shell clusters.

• Acid-Base-Triggered Structural Transformation of a Polyoxometalate Core Inside a Dodecahedrane-like Silver Thiolate Shell,
  Hong Liu, Chao-Yu Song, Ren-Wu Huang, Yu Zhang, Hong Xu, Mei-Jia Li, Shuang-Quan Zang, Guang-Gang Gao,
  Angew. Chem. Int. Ed. 2016.
  DOI: 10.1002/anie.201511765