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Pyramidal Heteroanion-Directed and Reduced MoV-Driven Assembly of Multi-Layered Polyoxometalate Cages
Preprints are manuscripts made publicly available before they have been submitted for formal peer review and publication. They might contain new research findings or data. Preprints can be a draft or final version of an author's research but must not have been accepted for publication at the time of submission.
submitted on 21.12.2018 and posted on 21.12.2018by 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.