Publication detail

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

Wu, SZ. Zurauskas, J. Domanski, M. Hitzfeld, PS. Butera, V. Scott, DJ. Rehbein, J. Kumar, A. Thyrhaug, E. Hauer, J. Barham, JP.

Original Title

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

Type

journal article in Web of Science

Language

English

Original Abstract

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).

Keywords

C-H AMINATION; ORGANIC ELECTROSYNTHESIS; LIGHT; DYNAMICS; ELECTROCHEMISTRY; REDUCTION; OXIDATION; STATES

Authors

Wu, SZ.; Zurauskas, J.; Domanski, M.; Hitzfeld, PS.; Butera, V.; Scott, DJ.; Rehbein, J.; Kumar, A.; Thyrhaug, E.; Hauer, J.; Barham, JP.

Released

21. 3. 2021

Publisher

ROYAL SOC CHEMISTRY

Location

CAMBRIDGE

ISBN

2052-4129

Periodical

Organic Chemistry Frontiers

Year of study

8

Number

6

State

People's Republic of China

Pages from

1

Pages to

12

Pages count

12

URL

https://pubs.rsc.org/en/content/articlelanding/2021/QO/D0QO01609H#!divAbstract

BibTex

@article{BUT171854,
  author="Wu, SZ. and Zurauskas, J. and Domanski, M. and Hitzfeld, PS. and Butera, V. and Scott, DJ. and Rehbein, J. and Kumar, A. and Thyrhaug, E. and Hauer, J. and Barham, JP.",
  title="Hole-mediated photoredox catalysis: tris(p-substituted)biarylaminium radical cations as tunable, precomplexing and potent photooxidants",
  journal="Organic Chemistry Frontiers",
  year="2021",
  volume="8",
  number="6",
  pages="1--12",
  doi="10.1039/d0qo01609h",
  issn="2052-4129",
  url="https://pubs.rsc.org/en/content/articlelanding/2021/QO/D0QO01609H#!divAbstract"
}