Self-assembly of an unprecedented polyoxomolybdate anion [Mo20O66](12-) in a giant peanut-like 62-core silver-thiolate nanocluster

A polyoxometalate-templated silver thiolate nanocluster, [Ag-62-((SBu)-Bu-t)(40)(Mo20O66)(Mo6O19)(3)(CH3CN)(2)]center dot(CF3SO3)(4) (1), has been isolated, in which a giant peanut-like silver(I)-thiolate cluster [Ag-62((SBu)-Bu-t)(40)](22+) encapsulates an unprecedented [Mo20O66](12-) polyoxoanion core. It opens a new approach for the synthesis of both elusive polyoxometalates and high-nuclearity silver(I)-thiolate nanoclusters.