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I19-Small Molecule Single Crystal Diffraction	Anisotropic polyoxometalate cages assembled via layers of heteroanion templates Qi Zheng , Manuel Kupper , Weimin Xuan , Hirofumi Oki , Ryo Tsunashima , De-Liang Long , Leroy Cronin Journal Of The American Chemical Society DOI: 10.1021/jacs.9b04533 Diamond Proposal Number(s): [18953] Open Access Show Abstract ▼ 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.	Jul 2019

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I19-Small Molecule Single Crystal Diffraction

Anisotropic polyoxometalate cages assembled via layers of heteroanion templates

Qi Zheng , Manuel Kupper , Weimin Xuan , Hirofumi Oki , Ryo Tsunashima , De-Liang Long , Leroy Cronin

Journal Of The American Chemical Society

DOI: 10.1021/jacs.9b04533

Diamond Proposal Number(s): [18953]