Buday, PhilippPhilippBudayKasahara, ChizuruChizuruKasaharaHofmeister, ElisabethElisabethHofmeisterKowalczyk, DanielDanielKowalczykFarh, Micheal K.Micheal K.FarhRiediger, SaskiaSaskiaRiedigerSchulz, MartinMartinSchulzWächtler, MariaMariaWächtlerFurukawa, ShunsukeShunsukeFurukawaSaito, MasaichiMasaichiSaitoZiegenbalg, DirkDirkZiegenbalgGräfe, StefanieStefanieGräfeBäuerle, PeterPeterBäuerleKupfer, StephanStephanKupferDietzek‐Ivanšić, BenjaminBenjaminDietzek‐IvanšićWeigand, WolfgangWolfgangWeigand2023-01-042023-01-042022https://publica.fraunhofer.de/handle/publica/43058810.1002/anie.2022020792-s2.0-8512684345935178850Inspired 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 π-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 [FeIFe0] species-in accordance with theoretical calculations-presumably driving photocatalysis effectively (TON≈210).enH2 ProductionOligothiopheneOperando EPR SpectroscopyPhotocatalysis[FeFe] Hydrogenase Mimicsjournal article