Issue 41, 2019

Synthesis, structure and electrochemical characterization of an isopolytungstate (W4O16) held by MnII anchors within a superlacunary crown heteropolyanion {P8W48}

Abstract

An isopolyanion {W4O16} within an archetypal {P8W48} heteropolyanion assembly [(P8W48O184)(W4O16)K10Li4Mn10Na(H2O)50Cl2]15− (Mn10W4-P8W48) has been synthesized by the reaction of the cyclic superlacunary anion [H7P8W48O184]33− and Mn(ClO4)2·6H2O in 1 M LiCl solution medium at pH 8. The isolated compound has been characterized by single-crystal X-ray crystallography, powder X-ray diffraction (PXRD), Fourier-transform infrared (FTIR) spectroscopy, elemental analysis and thermogravimetric analysis. Electrochemical studies were also performed on Mn10W4-P8W48, which confirmed the presence of Mn centres bonded to the tungstic framework. The novel polyanion [(P8W48O184)(W4O16)K10Li4Mn10Na(H2O)50Cl2]15− is the first example of a macrocyclic complex, where an isopolyanion (W4O16)8− is embedded within the inner cavity of {P8W48} and is placed in position by six MnII cations as anchors, whereas the exocyclic coordination of four further MnII cations to {P8W48} yields an extended structure by linking neighbouring polyanions through {W–O–Mn–O–W} bridges. Furthermore, the polyanion Mn10W4-P8W48 is the first derivative of {P8W48} with six MnII ions (largest) coordinated to the inner side of the crown ring as anchors.

Graphical abstract: Synthesis, structure and electrochemical characterization of an isopolytungstate (W4O16) held by MnII anchors within a superlacunary crown heteropolyanion {P8W48}

Supplementary files

Article information

Article type
Paper
Submitted
12 Jūn. 2019
Accepted
15 Jūl. 2019
First published
16 Jūl. 2019
This article is Open Access
Creative Commons BY-NC license

Dalton Trans., 2019,48, 15545-15552

Synthesis, structure and electrochemical characterization of an isopolytungstate (W4O16) held by MnII anchors within a superlacunary crown heteropolyanion {P8W48}

M. Ibrahim, I. M. Mbomekallé, P. de Oliveira, G. E. Kostakis and C. E. Anson, Dalton Trans., 2019, 48, 15545 DOI: 10.1039/C9DT02478F

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