Experimental and Theoretical Investigation of the Light‐Driven Hydrogen Evolution by Polyoxometalate–Photosensitizer Dyads

Abstract

The visible-light-driven hydrogen evolution reaction (HER) by covalent photosensitizer-catalyst dyads is one of the most elegant concepts in supramolecular homogeneous solar energy conversion. The intricacies of catalyst reactivity and photosensitizer-catalyst interactions require a detailed fundamental understanding of the system to rationalize the observed reactivities. Here, we report three dyads based on the covalent imine-bond linkage of an iridium photosensitizer and an organo-functionalized Anderson polyoxometalate anion [MMo₆ O₁₈ {(OCH₂ )₃ CNH₂ }₂ ]^3- (M=Mn³⁺ , Fe³⁺ , Co³⁺ ). Modification of the central metal ion M is used to modulate the HER activity. Detailed theoretical and experimental studies examine the role of the central metal ion M and provide critical understanding of the redox activity and light-driven HER activity of the novel dyads. Thus, the study enables a knowledge-based optimization of HER dyads by chemical modification of the reactive metal oxide components.