Evidence and Governing Factors of the Radical-Ion Photoredox Catalysis

Dong Yeun Jeong, Da Seul Lee, Ha Lim Lee, Sanghee Nah, Jun Yeob Lee, Eun Jin Cho, Youngmin You

Research output: Contribution to journalArticlepeer-review

26 Scopus citations


Photoinduced electron transfer of a radical species provides a promising strategy for expanding the scope of photoredox catalysis. However, the mechanism underlying the radical-ion photoredox catalysis has yet been fully established. In the present research, we investigated the generation and annihilation of the key catalytic intermediate in the borylation reaction of aryl halides. To disentangle the intricate catalysis cycle, we conducted experiments using electrochemical, transient absorption and photoluminescence spectroscopy and quantum chemical calculation techniques. Our mechanistic studies provided convincing evidence that the active catalyst species is the excited-state radical anion. We also found that the catalyst activation is retarded by multiple annihilative processes, among which the intrinsic relaxation of the excited-state radical anion of the catalyst is the most destructive. We expect these mechanistic findings will guide the future development of photoredox catalysis of radical species.

Original languageEnglish
Pages (from-to)6047-6059
Number of pages13
JournalACS Catalysis
Issue number10
StatePublished - 20 May 2022

Bibliographical note

Funding Information:
This work was supported by the Midcareer Research Program (NRF-2019R1A2C2003969 and NRF-2020R1A2C2009636) and the Basic Research Laboratory Program (NRF-2019R1A4A1029052) through National Research Foundation grants funded by the Ministry of Science, Information, and Communication Technology and Future Planning.

Publisher Copyright:
© 2022 American Chemical Society.


  • borylation
  • deactivation
  • mechanism
  • photoredox catalysis
  • radical ion


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