Multifunctional Polyoxometalate Platforms for Supramolecular Light-Driven Hydrogen Evolution**

in: Chemistry-A European Journal (2021)
Maloul, Salam; van den Borg, Matthias; Müller, Carolin; Zedler, Linda; Mengele, Alexander; Gaissmaier, Daniel; Jacob, Timo; Rau, Sven; Dietzek-Ivanšić, Benjamin; Streb, Carsten
Multifunctional supramolecular systems are a central research topic in light-driven solar energy conversion. Here, we report a polyoxometalate (POM)-based supramolecular dyad, where two platinum-complex hydrogen evolution catalysts are covalently anchored to an Anderson polyoxomolybdate anion. Supramolecular electrostatic coupling of the system to an iridium photosensitizer enables visible light-driven hydrogen evolution. Combined theory and experiment demonstrate the multifunctionality of the POM, which acts as photosensitizer/catalyst-binding-site[1] and facilitates light-induced charge-transfer and catalytic turnover. Chemical modification of the Pt-catalyst site leads to increased hydrogen evolution reactivity. Mechanistic studies shed light on the role of the individual components and provide a molecular understanding of the interactions which govern stability and reactivity. The system could serve as a blueprint for multifunctional polyoxometalates in energy conversion and storage.

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