Issue 21, 2022

Composition-driven archetype dynamics in polyoxovanadates

Abstract

Molecular metal oxides often adopt common structural frameworks (i.e. archetypes), many of them boasting impressive structural robustness and stability. However, the ability to adapt and to undergo transformations between different structural archetypes is a desirable material design feature offering applicability in different environments. Using systems thinking approach that integrates synthetic, analytical and computational techniques, we explore the transformations governing the chemistry of polyoxovanadates (POVs) constructed of arsenate and vanadate building units. The water-soluble salt of the low nuclearity polyanion [V6As8O26]4− can be effectively used for the synthesis of the larger spherical (i.e. kegginoidal) mixed-valent [V12As8O40]4− precipitate, while the novel [V10As12O40]8− POVs having tubular cyclic structures are another, well soluble product. Surprisingly, in contrast to the common observation that high-nuclearity polyoxometalate (POM) clusters are fragmented to form smaller moieties in solution, the low nuclearity [V6As8O26]4− anion is in situ transformed into the higher nuclearity cluster anions. The obtained products support a conceptually new model that is outlined in this article and that describes a continuous evolution between spherical and cyclic POV assemblies. This new model represents a milestone on the way to rational and designable POV self-assemblies.

Graphical abstract: Composition-driven archetype dynamics in polyoxovanadates

Supplementary files

Article information

Article type
Edge Article
Submitted
16 Febr. 2022
Accepted
29 Apr. 2022
First published
29 Apr. 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2022,13, 6397-6412

Composition-driven archetype dynamics in polyoxovanadates

A. Kondinski, M. Rasmussen, S. Mangelsen, N. Pienack, V. Simjanoski, C. Näther, D. L. Stares, C. A. Schalley and W. Bensch, Chem. Sci., 2022, 13, 6397 DOI: 10.1039/D2SC01004F

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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