The chemistry of Ce-based metal–organic frameworks

Metal-organic frameworks (MOFs) have gained widespread attention due to their modular construction that allows the tuning of their properties. Within this vast class of compounds, metal carboxylates containing tri- and tetravalent metal ions have been in the focus of many studies due to their often high thermal and chemical stabilities. Cerium has a rich chemistry, which depends strongly on its oxidation state. Ce(iii) exhibits properties typically observed for rare earth elements, while Ce(iv) is mostly known for its oxidation behaviour. In MOF chemistry this is reflected in their unique optical and catalytic properties. The synthetic parameters for Ce(iii)- and Ce(iv)-MOFs also differ substantially and conditions must be chosen to prevent reduction of Ce(iv) for the formation of the latter. Ce(iii)-MOFs are usually reported in comprehensive studies together with those constructed with other RE elements and normally they are isostructural. They exhibit a greater structural diversity, which is reflected in the larger variety of inorganic building units. In contrast, the synthesis conditions of Ce(iv)-MOFs were only recently (2015) established. These lead selectively to hexanuclear Ce-O clusters that are well-known for Zr-MOFs and therefore very similar structural and isoreticluar chemistry is found. Hence Ce(iv)-MOFs exhibit often high porosity, while only a few porous Ce(iii)-MOFs have been described. Some of these show structural flexibility which makes them interesting for separation processes. For Ce(iv)-MOFs the redox properties are most relevant. Thus, they are intensively discussed for catalytic, photocatalytic and sensing applications. In this perspective, the synthesis, structural chemistry and properties of Ce-MOFs are summarized.