Anisotropic Polyoxometalate Cages Assembled Via Layers of Heteroanion Templates

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2019 Jul 12

PMID 31295408

Citations 2

Authors

Qi Zheng

Manuel Kupper

Weimin Xuan

Hirofumi Oki

Ryo Tsunashima

De-Liang Long

Leroy Cronin

Affiliations

Soon will be listed here.

Abstract

The synthesis of anisotropic redox-active polyoxometalates (POMs) that can switch between multiple states is critical for understanding the mechanism of assembly of structures with a high aspect ratio, as well as for their application in electronic devices. However, a synthetic methodology for the controlled growth of such clusters is lacking. Here we describe a strategy, using the heteroanion-directed assembly, to produce a family of 10 multi-layered, anisotropic POM cages templated by redox-active pyramidal heteroanions with the composition [WMoO(XO)], [WMoO(XO)], and [WMoO(XO)] for the double, triple, and quadruple layered clusters, respectively. It was found that the introduction of reduced molybdate is essential for self-assembly and results in mixed-metal (W/Mo) and mixed-valence (W/Mo) POM cages, as confirmed by an array of analytical techniques. To probe the archetype in detail, a tetrabutyl ammonium (TBA) salt derivative of a fully oxidized two-layered cage is produced as a model structure to confirm that all the cages are a statistical mixture of isostructures with variable ratios of W/Mo. Finally, it was found that multilayered POM cages exhibit dipolar relaxations due to the presence of the mixed valence W/Mo metal centers, demonstrating their potential use for electronic materials.

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