Mo72Fe30 Keplerate encapsulating a PMo12 Keggin anion

Cation-uptake has been long researched as an important topic in materials science. Herein we focus on a molecular crystal composed of a charge-neutral polyoxometalate (POM) capsule [MoVI72FeIII30O252(H2O)102(CH3CO2)15]3+ encapsulating a Keggin-type phosphododecamolybdate anion [α-PMoVI12O40]3−. Cation-coupled electron-transfer reaction occurs by treating the molecular crystal in an aqueous solution containing CsCl and ascorbic acid as a reducing reagent. Specifically, multiple Cs+ ions and electrons are captured in crown-ether-like pores {MoVI3FeIII3O6}, which exist on the surface of the POM capsule, and Mo atoms, respectively. The locations of Cs+ ions and electrons are revealed by single-crystal X-ray diffraction and density functional theory studies. Highly selective Cs+ ion uptake is observed from an aqueous solution containing various alkali metal ions. Cs+ ions can be released from the crown-ether-like pores by the addition of aqueous chlorine as an oxidizing reagent. These results show that the POM capsule functions as an unprecedented “redox-active inorganic crown ether”, clearly distinguished from the non-redox-active organic counterpart.

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