Investigation of the Ultrafast Dynamics Occurring during Unsensitized Photocatalytic H<sub>2</sub> Evolution by an [FeFe]-Hydrogenase Subsite Analogue

Frederix, Pim W. J. M.; Adamczyk, Katrin; Wright, Joseph A.; Tuttle, Tell; Ulijn, Rein V.; Pickett, Christopher J.; Hunt, Neil T.

doi:10.1021/om500521w

Cited by 24 publications

(38 citation statements)

References 32 publications

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“…However, TD-DFT work suggested that excitation was more likely to result in photolysis or gross deformation of the core geometry leading to a more terminal Fe-H species [145]. Based on this theoretical work and their own time-resolved infrared spectroscopic investigation, Hunt, Pickett, and coworkers suggested that a CO is photolabile [146]. The CO-depleted photoproduct may be the active catalyst.…”

Section: Photocatalytic Production Of Hydrogenmentioning

confidence: 98%

Biomimetic Complexes for Production of Dihydrogen and Reduction of CO2

Jennings

Laureanti

Jones

2015

Homo- And Heterobimetallic Complexes in Catalysis

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The active sites of several bioenergetically important metalloenzymes that perform multielectron redox reactions feature heterobimetallic complexes. Herein, we review recent understanding of the structure and mechanisms of hydrogenases, formate dehydrogenases, and carbon monoxide dehydrogenases. Then we evaluate progress toward creating functional, small-molecule complexes that reproduce the activities of these active sites. Particular emphasis is placed on comparing catalytic properties including turnover number, turnover frequency, required overpotential, and catalyst stability. Opportunities and challenges for future work are also considered.

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Section: Photocatalytic Production Of Hydrogenmentioning

confidence: 98%

Biomimetic Complexes for Production of Dihydrogen and Reduction of CO2

Jennings

Laureanti

Jones

2015

Homo- And Heterobimetallic Complexes in Catalysis

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“…Multicomponent systems with commonly used organometallic photosensitizers of either Ru, Re, Rh, or Ir have been reported . For some sensitizer–catalyst dyads, in which a light harvester is covalently linked to a [FeFe]‐H 2 ase mimic, photocatalysis has been shown to be driven at moderate turnover numbers (TON<127) . Furthermore, complete hybrid artificial photosynthetic systems, dendrimer‐based systems, ZnS nanoparticles, or quantum dots, as light harvesters have also been reported.…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, complete hybrid artificial photosynthetic systems, dendrimer‐based systems, ZnS nanoparticles, or quantum dots, as light harvesters have also been reported. More recently, an unsensitized protonated model capable of absorbing light energy and catalyzing H 2 formation has been characterized …”

Section: Introductionmentioning

confidence: 99%

“…[17][18][19][20][21][22][23][24] For some sensitizer-catalyst dyads, in whichalight harvester is covalently linked to a[ FeFe]-H 2 ase mimic, photocatalysis has been shown to be driven at moderate turnover numbers (TON < 127). [25][26][27][28][29][30] Furthermore, complete hybrida rtificial photosynthetic systems, [31] dendrimer-based systems, [32] ZnS nanoparticles, [33] or quantum dots, [34,35] as light harvesters have also been reported. More recently,a nu nsensitized protonated model capable of absorbingl ight energy and catalyzing H 2 formation has been characterized.…”

Section: Introductionmentioning

confidence: 99%

“…More recently,a nu nsensitized protonated model capable of absorbingl ight energy and catalyzing H 2 formation has been characterized. [29,36] An entire spectrum of [FeFe]-H 2 ase mimics have been established,b ut most of them are only soluble in organic solvents or mixtures of organic solvents and water.T oconductphotoca-talyticH 2 generation in aqueousm edia, such hydrophobic catalysts or sensitizer-catalyst dyads mustb ei ncorporated within the supramolecular systemsw ith high affinity to aqueous media such as micelles, [37][38][39] cyclodextrins, [40] metal-organic frameworks, [41][42][43] molecular thieves, [44] or hydrogels [45] as solidsupported molecular catalysts seems to be feasible approaches.…”

Section: Introductionmentioning

confidence: 99%

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Photocatalytic Hydrogen Evolution Driven by [FeFe] Hydrogenase Models Tethered to Fluorene and Silafluorene Sensitizers

Goy

Bertini

Rudolph

et al. 2016

Chemistry A European J

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It is successfully shown that photocatalytic proton reduction to dihydrogen in the presence of a sacrificial electron donor, such as trimethylamine (TEA) and ascorbate, can be driven by compact sensitizer-catalyst dyads, that is, dithiolate-bridged [FeFe] hydrogenase models tethered to organic sensitizers, such as fluorenes and silafluorenes (1 a-4 a). The sensitizer-catalyst dyads 1 a-4 a show remarkable and promising catalytic activities as well as enhanced stabilities during photocatalysis performed under UV-light irradiation. The photocatalysis was carried out both in non-aqueous and aqueous media. The latter experiments were performed by solubilizing the photocatalysts within micelles formed by either sodium dodecyl sulfate (SDS) or cetyltrimethylammonium bromide (CTAB). In this study a turnover number of 539 (7 h) is achieved under optimized conditions, which corresponds to an exceptionally high turnover frequency of 77 h . Theoretical investigations as well as emission decay experiments were performed to understand the observed phenomena together with the mechanisms of photocatalytic H generation.

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On the photochemistry of Fe₂(edt)(CO)₄(PMe₃)₂, a [FeFe]‐hydrogenase model: A DFT/TDDFT investigation

Bertini

Alberto

Arrigoni

et al. 2017

Int J of Quantum Chemistry

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The photochemistry of the [FeFe] hydrogenases model [Fe 2 (edt)(CO) 4 (PMe 3 ) 2 ] (edt 5 1-2 ethanedithiolate, (1) is investigated at Time-Dependent Density Functional Theory (TDDFT) level, focusing on the effect of the phosphine ligands on the early stages of the photodynamic of the system compared to that of the all CO model Fe 2 (pdt)(CO) 6 (2) (pdt 5 1-3 propanedithiolate). We observed a role of the Fe!S charge transfer for the lower energy singlet transitions, unveiling a photoisomerization pathway between the lowest energy forms while the higher energy excitations are likely involved in the CO dissociation pathways. TDDFT shows that the average Fe-CO bond elongation in 1 is shorter than that observed in 2, providing the electronic structure rationale on the observation that diiron dithiolates are more photo-stable with respect to the CO photolysis than the all CO model. This is relevant for catalyst photo-stability and is an advantageous and thus desirable feature for practical applications of photo-hydrogen evolution. K E Y W O R D S diiron models, excited states, [Fe-Fe]-hydrogenases, photolysis, TDDFT 1 | I N TR ODU C TI ON [Fe 2 (edt)(CO) 4 (PMe 3 ) 2 ] (edt 5 1-2 ethan-dithiolate and PMe 3 5 trimethylphosphine) (1) is a biomimetic model of [FeFe]-hydrogenases active site that belongs to the general family of compounds with formula [Fe 2 (SRS)(CO) 6n (L) n ] (SRS 5 dithiolate bidentate ligand; L 5 CO, CN -, PR 3 , SR -, ecc) .Hydrogenases are metallo-enzymes which reversibly catalyze the H 2 ! 2H 1 1 2eoxidation; [FeFe]-hydrogenases are one of the three classes of hydrogenases and catalyze preferentially the proton reduction with an extraordinary high H 2 evolution activity.[FeFe]-hydrogenases active site is called H-Cluster (see Figure 1) and features a Fe 6 S 6 cluster made by a canonical cubane Fe 4 S 4 cluster bound to a Fe 2 S 2 binuclear cluster. The latter provides the binding site of the substrates (H 2 or H 1 ), where actually the catalysis occurs.Fe 2 S 2 subcluster is the organometallic portion of the H-cluster in which the 2 iron atoms are coordinated by non-protein CO and CNligands, and additionally bridged by a 1-3 azadithiolate ligand (ASCH 2 ANHACH 2 SA). The peculiar inverted square pyramids edge-shared coordination of the Fe atoms leaves one free coordination position for substrates binding to the Fe atom distal with respect to the cubane.Int J Quantum Chem. 2018;118:e25537.

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Investigation of the Ultrafast Dynamics Occurring during Unsensitized Photocatalytic H₂ Evolution by an [FeFe]-Hydrogenase Subsite Analogue

Cited by 24 publications

References 32 publications

Biomimetic Complexes for Production of Dihydrogen and Reduction of CO2

Biomimetic Complexes for Production of Dihydrogen and Reduction of CO2

Photocatalytic Hydrogen Evolution Driven by [FeFe] Hydrogenase Models Tethered to Fluorene and Silafluorene Sensitizers

On the photochemistry of Fe₂(edt)(CO)₄(PMe₃)₂, a [FeFe]‐hydrogenase model: A DFT/TDDFT investigation

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Investigation of the Ultrafast Dynamics Occurring during Unsensitized Photocatalytic H2 Evolution by an [FeFe]-Hydrogenase Subsite Analogue

Cited by 24 publications

References 32 publications

Biomimetic Complexes for Production of Dihydrogen and Reduction of CO2

Biomimetic Complexes for Production of Dihydrogen and Reduction of CO2

Photocatalytic Hydrogen Evolution Driven by [FeFe] Hydrogenase Models Tethered to Fluorene and Silafluorene Sensitizers

On the photochemistry of Fe2(edt)(CO)4(PMe3)2, a [FeFe]‐hydrogenase model: A DFT/TDDFT investigation

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Investigation of the Ultrafast Dynamics Occurring during Unsensitized Photocatalytic H₂ Evolution by an [FeFe]-Hydrogenase Subsite Analogue

On the photochemistry of Fe₂(edt)(CO)₄(PMe₃)₂, a [FeFe]‐hydrogenase model: A DFT/TDDFT investigation