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Anisotropic polyoxometalate cages assembled via layers of heteroanion templates

DOI: 10.1021/jacs.9b04533 DOI Help

Authors: Qi Zheng (The University of Glasgow) , Manuel Kupper (The University of Glasgow) , Weimin Xuan (The University of Glasgow) , Hirofumi Oki (Yamaguchi University) , Ryo Tsunashima (Yamaguchi University) , De-Liang Long (The University of Glasgow) , Leroy Cronin (The University of Glasgow)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society

State: Published (Approved)
Published: July 2019
Diamond Proposal Number(s): 18953

Open Access Open Access

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 ten multi-layered anisotropic POM cages templated redox-active pyramidal heteroanions with the composition [W16Mo2O54(XO3)]n-,[W21Mo3O75(XO3)2]m-,[W26Mo4O93(XO3)3]o- for the single, double and triple layered clusters respectively. It was found that the introduction of reduced molybdate is essential for self-assembly of and results in mixed-metal (W/Mo) and mixed-valence (WVI/MoV) 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 multi-layered POM cages exhibit dipolar relaxations due to the presence of the mixed valence WVI/MoV metal centers, demonstrating their potential use for electronic materials.

Journal Keywords: Crystals; Granular materials; Sodium; Vinyl; Cluster chemistry

Subject Areas: Chemistry, Materials

Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 17/07/2019 14:30


Discipline Tags:

Chemistry Chemical Engineering Engineering & Technology Inorganic Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)