Combining energy and electron transfer in a supramolecular environment for the “green” generation and utilization of hydrated electrons through photoredox catalysis

Kerzig, Christoph; Goez, Martin

doi:10.1039/c5sc04800a

Cited by 75 publications

(95 citation statements)

References 42 publications

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“…Many polycyclic aromatic hydrocarbon (PAH) compounds have triplet states near the lowest 3 MLCT state of common d 6 metal emitters such as Ru II polypyridines or cyclometalated Ir III complexes, and in such cases, TTET often results in the rapid formation of 3* A exhibiting very long lifetimes . When 3* A is quenched reductively with sacrificial electron donors, A .− forms, and this highly reducing PAH radical anion can potentially be used directly for photoredox chemistry, or A .− can be excited further to produce even more strongly reducing hydrated electrons (Figure ) …”

Section: The Third Level: Separating Primary and Secondary Absorbermentioning

confidence: 99%

Multi‐Photon Excitation in Photoredox Catalysis: Concepts, Applications, Methods

2020

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The energy of visible photons and the accessible redox potentials of common photocatalysts set thermodynamic limits to photochemical reactions that can be driven by traditional visible‐light irradiation. UV excitation can be damaging and induce side reactions, hence visible or even near‐IR light is usually preferable. Thus, photochemistry currently faces two divergent challenges, namely the desire to perform ever more thermodynamically demanding reactions with increasingly lower photon energies. The pooling of two low‐energy photons can address both challenges simultaneously, and whilst multi‐photon spectroscopy is well established, synthetic photoredox chemistry has only recently started to exploit multi‐photon processes on the preparative scale. Herein, we have a critical look at currently developed reactions and mechanistic concepts, discuss pertinent experimental methods, and provide an outlook into possible future developments of this rapidly emerging area.

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Section: The Third Level: Separating Primary and Secondary Absorbermentioning

confidence: 99%

Multi‐Photon Excitation in Photoredox Catalysis: Concepts, Applications, Methods

2020

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“…This benefit is given af urther boost by the low radical concentrations attained with LED illumination. Hence,photoredox catalysis is inherently well-suited for accommodating photon pooling as an accessory; [3,21,22] and it is expected to perform this function better than two-photon processes without intervening electron transfer, [1] even when they are catalytic. [2,23] Thec atalyst of this work is the popular ruthenium-trisbipyridyl ion [Ru(bpy) 3 ] 2+ .…”

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confidence: 99%

Generating Hydrated Electrons for Chemical Syntheses by Using a Green Light‐Emitting Diode (LED)

2018

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We present the first working system for accessing and utilizing laboratory-scale concentrations of hydrated electrons by photoredox catalysis with a green light-emitting diode (LED). Decisive are micellar compartmentalization and photon pooling in an intermediate that decays with second-order kinetics. The only consumable is the nontoxic and bioavailable vitamin C. A turnover number of 1380 shows the LED method to be on par with electron generation by high-power pulsed lasers, but at a fraction of the cost. The extreme reducing power of the electron and its long unquenched life as a ground-state species are synergistic. We demonstrate the applicability to the dechlorination, defluorination, and hydrogenation of compounds that are inert towards all other visible-light photoredox catalysts known to date. A comprehensive mechanistic investigation from microseconds to hours yields results of general validity for photoredox catalysis with photon pooling, allowing optimization and upscaling.

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“…Das Konzept von Abbildung wurde erstmals für die Photoredoxkatalyse mit [Ru(bpy) 3 ] 2+ und einem carboxylierten Pyren (Py − ) in mizellarer Umgebung realisiert (Tabelle , Eintrag 1) . Sowohl der TTET zwischen dem 3 MLCT‐angeregten Ru II ‐Komplex und Py − als auch die reduktive 3 Py − ‐Löschung durch Asc 2− laufen mit hohen Geschwindigkeitskonstanten ab (>2×10 8 m −1 s −1 ).…”

Section: Die Dritte Ebene: Trennung Von Primärem Und Sekundärem Absorberunclassified

Multiphotonen‐Anregung in der Photoredoxkatalyse: Konzepte, Anwendungen und Methoden

2020

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Die Energie sichtbarer Photonen und die zugänglichen Redoxpotentiale üblicher Photokatalysatoren schränken die Anzahl derjenigen Photoreaktionen ein, die durch sichtbares Licht angetrieben werden können. Da UV‐Anregung schädlich ist und häufig Nebenreaktionen auslöst, ist sichtbares Licht oder sogar NIR‐Strahlung vorzuziehen. Die Photochemie befasst sich momentan mit einer zweischneidigen Herausforderung, und zwar mit dem Wunsch, immer thermodynamisch anspruchsvollere Reaktionen mit immer kleineren Photonenenergien durchführen zu können. Das Akkumulieren der Energie zweier energiearmer Photonen kann dazu passende Lösungsansätze liefern. Obwohl die Multiphotonen‐Spektroskopie gut etabliert ist, haben Photoredox‐Synthesechemiker erst kürzlich begonnen, Multiphotonen‐Prozesse präparativ zu nutzen. Hier werfen wir einen kritischen Blick auf kürzlich entwickelte Reaktionen und mechanistische Konzepte, diskutieren einschlägige experimentelle Methoden und geben einen Ausblick auf mögliche zukünftige Entwicklungen dieses jungen Forschungsgebiets.

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Combining energy and electron transfer in a supramolecular environment for the “green” generation and utilization of hydrated electrons through photoredox catalysis

Cited by 75 publications

References 42 publications

Multi‐Photon Excitation in Photoredox Catalysis: Concepts, Applications, Methods

Multi‐Photon Excitation in Photoredox Catalysis: Concepts, Applications, Methods

Generating Hydrated Electrons for Chemical Syntheses by Using a Green Light‐Emitting Diode (LED)

Multiphotonen‐Anregung in der Photoredoxkatalyse: Konzepte, Anwendungen und Methoden

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