Hole-mediated photoredox catalysis: tris(p-substituted)biarylaminium radical cations as tunable, precomplexing and potent photooxidants

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216305%3A26620%2F21%3APU141064" target="_blank" >RIV/00216305:26620/21:PU141064 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlelanding/2021/QO/D0QO01609H#!divAbstract" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2021/QO/D0QO01609H#!divAbstract</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d0qo01609h" target="_blank" >10.1039/d0qo01609h</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Hole-mediated photoredox catalysis: tris(p-substituted)biarylaminium radical cations as tunable, precomplexing and potent photooxidants

Popis výsledku v původním jazyce

As a combination of visible light photoredox catalysis and synthetic organic electrochemistry, electrochemically-mediated photoredox catalysis emerged as a powerful synthetic technique in recent years, overcoming fundamental limitations of electrochemistry and photoredox catalysis in the single electron transfer activation of small organic molecules. Herein we report a tunable class of electroactivated photoredox catalyst, tri(para-substituted)biarylamines, that become superoxidants in their photoexcited states even able to oxidize molecules beyond the solvent window limits of cyclic voltammetry (such as polyfluorobenzene and trifluorotoluene). Furthermore, we demonstrate that precomplexation not only permits the excited state photochemistry of tris(para-substituted)biarylaminium cations to overcome picosecond lifetime, but enables and rationalizes the surprising photochemistry of their higher-order doublet (D-n) excited states, unlocking extremely high oxidative potentials (up to a record-breaking similar to+4.4 V vs. SCE).

Název v anglickém jazyce

Hole-mediated photoredox catalysis: tris(p-substituted)biarylaminium radical cations as tunable, precomplexing and potent photooxidants

Popis výsledku anglicky

As a combination of visible light photoredox catalysis and synthetic organic electrochemistry, electrochemically-mediated photoredox catalysis emerged as a powerful synthetic technique in recent years, overcoming fundamental limitations of electrochemistry and photoredox catalysis in the single electron transfer activation of small organic molecules. Herein we report a tunable class of electroactivated photoredox catalyst, tri(para-substituted)biarylamines, that become superoxidants in their photoexcited states even able to oxidize molecules beyond the solvent window limits of cyclic voltammetry (such as polyfluorobenzene and trifluorotoluene). Furthermore, we demonstrate that precomplexation not only permits the excited state photochemistry of tris(para-substituted)biarylaminium cations to overcome picosecond lifetime, but enables and rationalizes the surprising photochemistry of their higher-order doublet (D-n) excited states, unlocking extremely high oxidative potentials (up to a record-breaking similar to+4.4 V vs. SCE).

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

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OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2021

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Organic Chemistry Frontiers

ISSN

2052-4110

e-ISSN

2052-4129

Svazek periodika

8

Číslo periodika v rámci svazku

6

Stát vydavatele periodika

CN - Čínská lidová republika

Počet stran výsledku

12

Strana od-do

1-12

Kód UT WoS článku

000631592900003

EID výsledku v databázi Scopus

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