Aqueous Bismuth Titanium–Oxo Sulfate Cluster Speciation and Crystallization

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 s...

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Bibliographic Details
Published in:Angewandte Chemie 2017-12, Vol.129 (51), p.16495-16499
Main Authors: Molina, Pedro I., Kozma, Karoly, Santala, Melissa, Falaise, Clément, Nyman, May
Format: Article
Language:English
Subjects:
Bismut
Bismuth
Chemistry
Clusters
Crystal structure
Crystallization
Electron microscopy
Intermediates
Light scattering
Metal oxides
Metall-Oxo-Cluster
Oxides
Photon correlation spectroscopy
Polyhedra
Polyoxokationen
Röntgenstreuung
Single crystals
Speciation
Sulfates
Titan
Titanium
Transmission electron microscopy
X-ray scattering
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Summary: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.[Ti22Bi7O41(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. Stabile Titan‐Oxo‐Cluster in Wasser: Titanoxysulfat ordnet sich beim Lösen in Wasser sofort zu monodispersen vielkernigen Clustern an. Gemäß Röntgenstreuung sind diese Cluster hoch labil und ohne klare innere Ordnung. Durch Versetzen mit Salpetersäure und BiIII werden sie schrittweise zersetzt; die resultierende Lösung enthält einen Heterometall‐Ti‐Oxo‐Cluster.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201709539