Design of Metal-Substituted Polyoxometalates as Sustainable Photocatalysts for the Development of Pharmaceutically Relevant Reactions.

We aim to develop metal-substituted polyoxometalates (Ms-POMs) as visible-light absorbing photocatalysts, and explore their application in pharmaceutically relevant reactions, such as Minisci-type reactions and the formation of amide bonds. Photoredox reactions are a growing strategy in green synthesis, but its dependence on noblemetal complexes (eg. Ru, Rh, Ir) or oxidation prone organic photocatalysts hampers its broader adoption by industry. On the other hand, readily available, stable and inexpensive POMs have been underexplored as photocatalysts despite their known photochemical properties. In this context, new POM photocatalysts will be developed by complexing them with transition metals, which render these complexes photoactive in the visible-light region. By combining metal and POM structure along with thorough characterization of photochemical properties, key structure-property relationships will be established and correlated with reactivity in model reactions. This new class of highly tunable inorganic photocatalysts featuring advantages such as great stability, tunable properties and easy recyclability will be used to develop green and useful photocatalytic reactions for medicinal chemistry. More specifically, Minisci-type reactions of underrepresented heteroarenes (quinazolines, [benz]imidazoles) and amide formations starting from readily available alcohols and amines are envisioned.