Catalysis

[FeFe] Hydrogenase based Prototype Photosensitizer-Catalyst Dyad for Hydrogen Generation under Visible Light

Authors

Abstract

Inspired by the active center of the natural [FeFe] hydrogenases, we designed a compact and precious metal-free photosensitizer-catalyst dyad (PS-CAT) for photocatalytic hydrogen evolution under visible light irradiation. PS-CAT represents a prototype dyad comprising pi-conjugated oligothiophenes as light absorbers. PS-CAT and its interaction with the sacrificial donor 1,3-dimethyl-2-phenylbenzimidazoline were studied by steady-state and time-resolved spectroscopy coupled with electrochemical techniques and visible light-driven photocatalytic investigations. Operando EPR spectroscopy revealed the formation of an active [Fe(I)Fe(0)] species – in accordance with theoretical calculations – presumably driving photocatalysis effectively (TON ≈ 210).

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Content

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Supplementary material

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Supporting Information
Materials and instrumentation, Synthesis and characterization, NMR spectra, Single crystal X-ray structure determination, Photocatalysis, UV-vis-monitored photocatalysis, Fluorescence quenching in presence of BIH, Time-resolved spectroscopy, EPR spectroscopy, Electrochemical characterization, Computational details, Crystallographic data have been deposited with the Cambridge Crystallographic Data Center as supplementary publication CCDC-2106348