Synthesis and characterisation of heterotrinuclear transition metal complexes for biomimetic proton reduction

Topf, Christoph; Kaiser, Manuel; Monkowius, Uwe; Knör, Günther

doi:10.1016/j.inoche.2017.01.032

Cited by 5 publications

(2 citation statements)

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“…S 0 )t ransitions in their UV/Vis/NIR and phosphorescence excitation spectra. [18] No attempts were made to measure ar eliable quantum yield for the NIR photolysis of complex 1 in aqueous solution. From the energy state model shown in Figure 6, however, ar easonablee stimate of F(NIR) can be derived.…”

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confidence: 99%

Spin‐Forbidden Excitation: A New Approach for Triggering Photopharmacological Processes with Low‐Intensity NIR Light

2017

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Exposure to low‐intensity radiation in the near‐infrared (NIR) spectral region matching the optically transparent “phototherapeutic window” of biological tissues can be applied to directly populate spin‐restricted excited states of light‐responsive compounds. This unconventional and unprecedented approach is introduced herein as a new strategy to overcome some of the major unresolved problems observed in the rapidly emerging fields of photopharmacology and molecular photomedicine, where practical applications in living cells and organisms are still limited by undesired side reactions and insufficient light penetration. Water‐soluble and biocompatible metal complexes with a significant degree of spin–orbit coupling were identified as target candidates for testing our new hypothesis. As a first example, a dark‐stable manganese carbonyl complex acting as a visible‐light‐triggered CO‐releasing molecule (Photo‐CORM) is shown to be photoactivated by NIR radiation, although apparently no spectroscopically evident absorption bands are detectable in this low‐energy region. This quite remarkable effect is ascribed to a strongly restricted, but obviously not completely forbidden optical population of the lowest triplet excited state manifold of the diamagnetic complex from the singlet ground state.

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confidence: 99%

Spin‐Forbidden Excitation: A New Approach for Triggering Photopharmacological Processes with Low‐Intensity NIR Light

2017

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“…[2] The vast amount of research that has been dedicated to mimicking the structure and/or functiono ft he active site has led to al arge number of enzymem imics for electroand photocatalytic hydrogen production. [3,4] Of particular interesti st he ability of the enzymet op reorganize protons and electrons in the vicinity of the actives ite. The actives ite consists of a[ 2Fe-2 S] cluster that functions as the proton reduction catalyst, and it is connected through a cysteiner esidue to a[ 4Fe-4 S] cluster,w hich in turn supplies electrons to the actives ite during catalysis.…”

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confidence: 99%

Photocatalytic Hydrogen Evolution by a Synthetic [FeFe] Hydrogenase Mimic Encapsulated in a Porphyrin Cage

Nurttila

Becker

Hessels

et al. 2018

Chemistry A European J

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The design of a biomimetic and fully base metal photocatalytic system for photocatalytic proton reduction in a homogeneous medium is described. A synthetic pyridylphosphole‐appended [FeFe] hydrogenase mimic was encapsulated inside a supramolecular zinc porphyrin‐based metal–organic cage structure Fe4(Zn‐L)6. The binding is driven by the selective pyridine–zinc porphyrin interaction and results in the catalyst being bound strongly inside the hydrophobic cavity of the cage. Excitation of the capsule‐forming porphyrin ligands with visible light while probing the IR spectrum confirmed that electron transfer takes place from the excited porphyrin cage to the catalyst residing inside the capsule. Light‐driven proton reduction was achieved by irradiation of an acidic solution of the caged catalyst with visible light.

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Advances in the chemistry of redox-active bis(imino)acenaphthenes (BIAN): A case of transition metal complexes

Fomenko,

Romashev,

Gushchin

2024

Coordination Chemistry Reviews

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Synthesis and characterisation of heterotrinuclear transition metal complexes for biomimetic proton reduction

Cited by 5 publications

References 15 publications

Spin‐Forbidden Excitation: A New Approach for Triggering Photopharmacological Processes with Low‐Intensity NIR Light

Spin‐Forbidden Excitation: A New Approach for Triggering Photopharmacological Processes with Low‐Intensity NIR Light

Photocatalytic Hydrogen Evolution by a Synthetic [FeFe] Hydrogenase Mimic Encapsulated in a Porphyrin Cage

Advances in the chemistry of redox-active bis(imino)acenaphthenes (BIAN): A case of transition metal complexes

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