Acid-Base-Triggered Structural Transformation of a Polyoxometalate Core Inside a Dodecahedrane-like Silver Thiolate Shell

Self-assembly of metavanadate and organosilver(I) salts leads to a novel dodecahedrane-like [Ag-30((BuS)-Bu-t)(20)](10+) silver(I) thiolate nanocage that tightly wraps an unusual C-2h polyoxovanadate anion. The polyoxovanadate core undergoes transformation to a D-3d configuration upon acidification, and reverts back to its original C-2h structure upon addition of base. Chromism was observed for the silver(I) thiolate cluster during the configurational change of the central polyoxovanadate core; the color of the solution changes reversibly from green to dark yellow. This work represents the first reported example of chromic polyoxometalate-templated silver(I) thiolate shells that respond to external acid-base stimuli. It also represents an important advance in providing crystallographic proof that structural transformations occur in a nanoscale core-shell cluster.