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

Abstract

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.

Insights into the different mechanistic stages of light-induced hydrogen evolution of a 5,5′-bisphenanthroline linked RuPt complex

“…As shown in several previous reports, replacement of the chloride ligands by iodide ligands typically enhances light-induced hydrogen evolution in Pt-based systems. 19,48,49 For instance, Kaufhold et al 48 showed that the addition of an iodide salt to the photocatalytic system can activate a platinum center during photocatalysis by in situ ligand exchange leading to improved H 2 formation.…”

Rational design and progress of molybdenum-oxo clusters

“…740 after 10 hours. 174 In 2022, the Yang group reported a pure-inorganic, bis-Sb 3 O 3 -functionalized Anderson–Evans complex, namely [Ni(H 2 O) 6 ]KH[NiMo 6 O 24 (Sb 3 O 3 ) 2 ]·5H 2 O (Fig. 18c).…”

Bi‐Functional On‐Surface Molecular Assemblies Predicted From a Multifaceted Computational Approach

“…This work is therefore relevant to the growing area of molecular spintronics, as well as the important topic of structure prediction for molecular materials in general. While bifunctional and multifunctional molecular assemblies have been reported in the experimental literature previously, [29,30] the prediction of a bifunctional assembly entirely from computation appears to be a first.…”