3 years ago

Aqueous Bismuth Titanium-Oxo Sulfate Cluster Speciation and Crystallization

Clement Falaise, Melissa Santala, Karoly Kozma, May Nyman, Pedro Molina
Inorganic aqueous metal-oxo clusters are both functional 'molecular metal-oxides', and intermediates to understand metal oxide growth from water. There has been a recent surge in discovery of aqueous Ti-oxo clusters but without extensive solution characterization. We use small-angle and total X-ray scattering, dynamic light scattering, transmission electron microscopy and single-crystal X-ray structure shows that heterometals (i.e. bismuth) stabilize labile Ti-oxo sulfate clusters in aqueous solution. We report [Ti22Bi7O41(OH)(OH2)30(SO4)12]2+ that features edge-sharing between the Ti and Bi polyhedra, different from the dominant corner-linking of Ti-oxo clusters. We propose that Bi stabilizes the Ti-polyhedra which are synergistically stabilized by the bidentate sulfates. Gained stability and potential functionality from heterometals is incentive to develop more broadly the landscape of heterometallic Ti-oxo clusters.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201709539

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