A Redox-active Inorganic Crown Ether Based on a Polyoxometalate Capsule

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2023 May 26

PMID 37234904

Authors

Nanako Tamai

Naoki Ogiwara

Eri Hayashi

Keigo Kamata

Toshiyuki Misawa

Takeru Ito

Tatsuhiro Kojima

Mireia Segado

Enric Petrus

Carles Bo

Sayaka Uchida

Affiliations

Soon will be listed here.

Abstract

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 [MoFeO(HO)(CHCO)] encapsulating a Keggin-type phosphododecamolybdate anion [α-PMoO]. 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 {MoFeO}, 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.

Citing Articles

Ce-mediated molecular tailoring on gigantic polyoxometalate {Mo} into half-closed {CeMo} for high proton conduction.

Li X, Li C, Hou M, Zhu B, Chen W, Sun C Nat Commun. 2023; 14(1):5025.

PMID: 37596263 PMC: 10439156. DOI: 10.1038/s41467-023-40685-0.

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