Manipulating the electronic properties of modular inorganic frameworks by introducing the right building blocks is an important goal for the development of electronically active materials. Polyoxometalates, nanosized oxide clusters of the early transition metals, provide a vast variety of compounds with useful applications and properties. We have reported a new type of modular framework material based purely on manganese substituted polyoxotungstate Keggin clusters, which are directly condensed without the use of additional linkers. The Mn(III)-centers are accessible for redox-chemistry, giving rise to reversible single crystal to single crystal transformation. Additionally, the kinetics of this process can be controlled by exchanging the heteroatom of the Keggin clusters from silicon to germanium. Herein, we present two new members of this family of compounds by substituting Mn(III)- for Co(II)-centers and we investigate their reactivity.

Configurable redox-properties in polyoxometalate-based
inorganic frameworks

239th National Meeting (2010)

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Configurable redox-properties in polyoxometalate-based inorganic frameworks