Activating a [FeFe] Hydrogenase Mimic for Hydrogen Evolution under Visible Light**

Buday, Philipp; Kasahara, Chizuru; Hofmeister, Elisabeth; Kowalczyk, Daniel; Farh, Micheal K.; Riediger, Saskia; Schulz, Martin; Wächtler, Maria; Furukawa, Shunsuke; Saito, Masaichi; Ziegenbalg, Dirk; Gräfe, Stefanie; Bäuerle, Peter; Kupfer, Stephan; Dietzek‐Ivanšić, Benjamin; Weigand, Wolfgang

doi:10.1002/anie.202202079

Cited by 13 publications

(26 citation statements)

References 43 publications

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“…In recent times, designing high-performance photosensitizers gained much attention from the scientific society. [1,[4][5][6][7][8][9][10][11][12][13] In this context, porphyrin-based sensitizers received great interest due to their high light-harvesting ability in the UV-Visible region, multiple redox states for attaining efficient photoinduced charge separation, and high photostability during photocatalysis. [1] Besides, their optoelectronic properties can be easily adjusted by integration of chromophores at four meso-positions of porphyrin macrocycle and insertion of various metals inside the porphyrin ring and consequently tailorable PHE properties.…”

Section: Introductionmentioning

confidence: 99%

Design of AIEgen‐based porphyrin for efficient heterogeneous photocatalytic hydrogen evolution

et al. 2023

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Tetraphenylethylene (TPE)‐conjugated porphyrin TPE‐ZnPF is synthesized in high yield and characterized by single‐crystal X‐ray diffraction. The propeller‐shaped TPE groups not only enable exceptional aggregation‐induced emission (AIE) in the solid state but also abolish the strong π‐π stacking of porphyrin moieties and thus prohibit aggregation‐caused quenching (ACQ). TPE‐ZnPF aggregates feature long‐lived photoexcited states, which subsequently suppress non‐radiative decay channels and enhance emission intensity. Moreover, its aggregates show more efficient light‐harvesting ability due to the Förster resonance energy transfer from the TPE energy donor to the porphyrin core energy acceptor, well‐defined nanosphere morphology, and more efficient photoinduced charge separation than the porphyrin Ph‐ZnPF, which possesses ACQ and agglomerated morphology. As a result, an excellent photocatalytic hydrogen evolution rate (ηH2) of 56.20 mmol g‒1 h‒1 is recorded for TPE‐ZnPF aggregates, which is 94‐fold higher than that of the aggregates of Ph‐ZnPF (0.60 mmol g‒1 h‒1) without the TPE groups.

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Section: Introductionmentioning

confidence: 99%

Design of AIEgen‐based porphyrin for efficient heterogeneous photocatalytic hydrogen evolution

et al. 2023

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“…This helps in understanding and improving, e.g., dyesensitized photocatalysis on surfaces, i.e., dye-sensitized photoelectrochemical cells [1][2][3][4] or dye-sensitized solar cells (DSSCs), [5][6][7] in light-driven catalysis, [8,9] energy storage, [10][11][12][13] and biomimetic photocatalytic systems. [14][15][16][17][18] Within the context of light-driven hydrogen formation, pioneering work by Kiwi and Grätzel [19] and subsequently, Sakai and Ozawa [20] did show that the combination of light absorption, charge transfer, and storage of redox equivalents on viologen-type molecules rendered highly active photocatalytic systems. Covalent linkage between viologen electron acceptors and catalytically active metal centers led to an overall improvement of catalytic activity with respect to attainable turnover numbers and frequencies.…”

Section: Introductionmentioning

confidence: 99%

“…This helps in understanding and improving, e.g., dye‐sensitized photocatalysis on surfaces, i.e., dye‐sensitized photoelectrochemical cells [ 1–4 ] or dye‐sensitized solar cells (DSSCs), [ 5–7 ] in light‐driven catalysis, [ 8,9 ] energy storage, [ 10–13 ] and biomimetic photocatalytic systems. [ 14–18 ]…”

Section: Introductionmentioning

confidence: 99%

Gatekeeping Effect of Ancillary Ligand on Electron Transfer in Click Chemistry‐Linked Tris‐Heteroleptic Ruthenium(II) Donor–Photosensitizer–Acceptor Triads

2023

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Stable charge‐separated states are key features for using light in various types of solar cells and a broad range of photocatalytic applications. So far, molecular systems often suffer from increased charge recombination after initial excitation. Herein, the scope of molecular model systems for intramolecular electron transfer and charge separation by applying copper‐catalyzed click chemistry to covalently functionalize tris‐heteroleptic ruthenium(II) complexes to yield donor–photosensitizer–acceptor triads with 1,4‐dihydro‐N‐benzyl‐nicotinamide (BNAH) as donor and N‐methyl‐4,4´‐bipyridinium (MQ+) as acceptor is studied. Two triads with electron‐withdrawing or electron‐donating ancillary 2,2´‐bipyridyl ligands are synthesized and their light‐induced intramolecular electron transfer and long‐lived charge‐separated states (τ = 0.8 ms and τ = 1.5 ms) are characterized using steady‐state and time‐resolved spectroscopy and electrochemistry. Additionally, it is found that the charge‐separated state resides on different parts of the molecule within these two triads, allowing for selective directionality of charge transfer within a molecule.

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“…High-performing photosensitizers and photocatalysts often contain noble metal complexes such as Ru(bpy) 3 2+ or Ir(ppy) 2 (bpy) + . , While the intrinsic charge-separated MLCT states of the noble metal complexes allow for prolongated excited-state lifetimes and decreased charge-recombination rates, chemical modifications and stability of these complexes are often limited. Though there is a need for the development of photocatalysts with straightforward modification strategies, only limited attempts of functionalizing molecular catalysts with organic dyes have been published; among them are BODIPY- or perylene-decorated cobaloximes , and oligothiophene-[FeFe] hydrogenase mimics . Recently, we introduced tetrasubstituted perylene monoimide dyes that not only have strong absorption of visible light and high photostability but also allow selective and orthogonal modifications of the chromophore that enable straightforward fine-tuning of their optical and electrochemical properties as well as their solubility. , By adding electron-withdrawing groups to intrinsically electron-poor perylene diimides, the electronic structure of the chromophore can be made even more electron deficient, which enables their applications as p-type semiconductors in dye-sensitized solar cells .…”

Section: Introductionmentioning

confidence: 99%

Bridging Platinum and Palladium to Bipyridine-Annulated Perylene for Light-Driven Hydrogen Evolution

Costabel

Jacobi

et al. 2023

ACS Catal.

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In this work, we present two bipyridine-annulated perylene tetracarboxylic ester (P-L) photocatalysts with PtCl2 and PdCl2. X-ray photoelectron spectroscopy showed that their binding energies match precisely the binding energies of the respective M(bpy)Cl2 complexes. Cyclic voltammetry measurements of the complexes displayed additional reduction potentials upon metal insertion. Light-driven catalysis demonstrated that both compounds are catalytically active, with P-Pt outcompeting P-Pd with a TON of 186 over 48 h in the presence of ascorbic acid (P-Pd: 50). Mercury poisoning experiments were carried out to validate the catalytically competent component. Almost quantitative quenching of the catalytic turnover was observed for P-Pd, whereas the hydrogen production rate remained unaffected for P-Pt, making it a photocatalyst that contains the structure PtN^NCl2 and nonetheless operates without a second noble metal nucleus or a separate photosensitizer under visible light. Time-resolved (fs and ns) spectroscopy on P-L and P-Pt yields insights into the light-induced intramolecular processes. In P-Pt, we observed that both 1IL (400 nm) and 1MLCT (500 nm) excitation leads to intersystem crossing with a solvent polarity-dependent distribution between 3MLCT and 3IL, where the 3IL population increases in ACN vs DCM, indicating that in aqueous catalytic samples, the 3IL state plays a major role in the catalytic process.

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Activating a [FeFe] Hydrogenase Mimic for Hydrogen Evolution under Visible Light**

Cited by 13 publications

References 43 publications

Design of AIEgen‐based porphyrin for efficient heterogeneous photocatalytic hydrogen evolution

Design of AIEgen‐based porphyrin for efficient heterogeneous photocatalytic hydrogen evolution

Gatekeeping Effect of Ancillary Ligand on Electron Transfer in Click Chemistry‐Linked Tris‐Heteroleptic Ruthenium(II) Donor–Photosensitizer–Acceptor Triads

Bridging Platinum and Palladium to Bipyridine-Annulated Perylene for Light-Driven Hydrogen Evolution

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