TitleAqueous Bismuth Titanium-Oxo Sulfate Cluster Speciation and Crystallization
Publication TypeJournal Article
Year of Publication2017
AuthorsMolina PI, Kozma K, Santala M, Falaise C, Nyman M
JournalAngewandte Chemie
Start Page16277
Date PublishedDecember 2017

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.