Aqueous Bismuth Titanium-Oxo Sulfate Cluster Speciation and Crystallization

Pedro I Molina; Karoly Kozma; Melissa Santala; Clément Falaise; May Nyman

doi:10.1002/anie.201709539

Aqueous Bismuth Titanium-Oxo Sulfate Cluster Speciation and Crystallization

Angew Chem Int Ed Engl. 2017 Dec 18;56(51):16277-16281. doi: 10.1002/anie.201709539. Epub 2017 Nov 24.

Authors

Pedro I Molina^{1

2}, Karoly Kozma¹, Melissa Santala³, Clément Falaise^{1

4}, May Nyman¹

Affiliations

¹ Department of Chemistry, Oregon State University, 107 Gilbert Hall, Corvallis, OR, 97331-4003, USA.
² Current address: Valliscor, Advanced Technology & Manufacturing Institute, 1110 NE Circle Blvd, Corvallis, USA.
³ Department of Mechanical, Industrial and Manufacturing Engineering, Oregon State University, USA.
⁴ Current address: Institut Lavoisier de Versailles, UMR 8180, UVSQ, Université Paris-Saclay, 78035, Versailles, France.

PMID: 29108099
DOI: 10.1002/anie.201709539

Abstract

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 a single-crystal X-ray structure to show that heterometals such as bismuth stabilize labile Ti-oxo sulfate clusters in aqueous solution.[Ti₂₂ Bi₇ O₄₁ (OH)(OH₂ )₃₀ (SO₄ )₁₂ ]²⁺ features edge-sharing between the Ti and Bi polyhedra, in contrast to the dominant corner-linking of Ti-oxo clusters. Bi stabilizes the Ti-polyhedra, which are synergistically stabilized by the bidentate sulfates. Gained stability and potential functionality from heterometals is an incentive to develop more broadly the landscape of heterometallic Ti-oxo clusters.

Keywords: X-ray scattering; bismuth; metal-oxo clusters; polyoxocations; titanium.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.