Rapid formation of small mixed-valence luminescent silver clusters via cation-coupled electron-transfer in a redox-active porous ionic crystal based on dodecamolybdophosphate.

Redox-active porous ionic crystals based on polyoxometalate (POM) were utilized to form and stabilize small mixed-valence luminescent silver clusters via cation-coupled electron-transfer (CCET) reactions. Reduction-induced ion-exchange between Cs+ and Ag+via CCET took less than 1 min to complete and consisted of two steps: electron transfer from reduced POM to Ag+ and the subsequent formation of a silver cluster, and diffusion of the silver cluster and exchange with Cs+. Notably, the simple ion-exchange took more than 24 h. The compound containing the silver cluster showed high affinity toward unsaturated hydrocarbon guests.