ChemRxiv
These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
preprint.pdf (3.11 MB)
0/0

Pyramidal Heteroanion-Directed and Reduced MoV-Driven Assembly of Multi-Layered Polyoxometalate Cages

preprint
submitted on 21.12.2018 and posted on 21.12.2018 by Qi Zheng,, Manuel Kupper, Weimin Xuan, Hirofumi Oki, Ryo Tsunashima, De-Liang Long, Leroy Cronin
The fabrication of redox-active polyoxometalates (POMs) that can switch between multiple states is critical for their application in electronic devices, yet, a sophisticated synthetic methodology is not well developed for such cluster types. Here we describe the heteroanion-directed and reduction-driven assembly of a series of multi-layered POM cages 1-10 templated by 1-3 redox-active pyramidal heteroanions. The heteroanions greatly affect the selfassembly of the resultant POM cages, leading to the generation of unprecedented three-layered peanut-shaped - 4, 7 and 8 - or bulletshaped - 5 and 6 - structures. The introduction of reduced molybdate is essential for the self-assembly of the compounds and results in mixed-metal (W/Mo), and mixed-valence (WVI/MoV) 1-10, as confirmed by redox titration, UV-Vis-NIR, NMR spectroscopy and mass spectrometry. 11, the tetrabutyl ammonium (TBA) salt derivative of the fully oxidized 3, is produced as a model structure for measurements to confirm that 1-10 are a statistical mixture of isostructural clusters with different ratios of W/Mo. Finally, multilayered POM cages exhibit dipole relaxations due to the presence of mixed valence WVI/MoV metal centers, demonstrating their potential uses for electronic materials.

History

Email Address of Submitting Author

lee.cronin@glasgow.ac.uk

Institution

University of Glasgow

Country

UK

ORCID For Submitting Author

0000-0001-8035-5757

Declaration of Conflict of Interest

none

Exports

Logo branding

Exports