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Title
Japanese:A redox-active inorganic crown ether based on a polyoxometalate capsule 
English:A redox-active inorganic crown ether based on a polyoxometalate capsule 
Author
Japanese: Nanako Tamai, Naoki Ogiwara, Eri Hayashi, Keigo Kamata, Toshiyuki Misawa, Takeru Ito, Tatsuhiro Kojima, Mireia Segado, Enric Petrus, Carles Bo, Sayaka Uchida.  
English: Nanako Tamai, Naoki Ogiwara, Eri Hayashi, Keigo Kamata, Toshiyuki Misawa, Takeru Ito, Tatsuhiro Kojima, Mireia Segado, Enric Petrus, Carles Bo, Sayaka Uchida.  
Language English 
Journal/Book name
Japanese:Chemical Science 
English:Chemical Science 
Volume, Number, Page Vol. 14    No. 20    pp. 5453-5459
Published date 2023 
Publisher
Japanese:Royal Society of Chemistry 
English:Royal Society of Chemistry 
Conference name
Japanese: 
English: 
Conference site
Japanese: 
English: 
Official URL https://doi.org/10.1039/D3SC01077E
 
DOI https://doi.org/10.1039/d3sc01077e
Abstract Cation-uptake has been long researched as an important topic in materials science. Herein we focus on a mol. crystal composed of a charge-neutral polyoxometalate (POM) capsule [MoVI72FeIII30O252(H2O)102(CH3CO2)15]3+ encapsulating a Keggin-type phosphododecamolybdate anion [ﾎｱ-PMoVI12O40]3-. Cation-coupled electron-transfer reaction occurs by treating the mol. 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, resp. The locations of Cs+ ions and electrons are revealed by single-crystal X-ray diffraction and d. 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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