Generation and Electron-Transfer Reactivity of the Long-Lived Photoexcited State of a Manganese(IV)-Oxo-Scandium Nitrate Complex

Namita Sharma, Yong Min Lee, Wonwoo Nam, Shunichi Fukuzumi

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5 Scopus citations

Abstract

Photoexcitation of a manganese(IV)-oxo-scandium nitrate complex ([(Bn-TPEN)MnIV(O)]2+−Sc(NO3)3) in a solvent mixture of trifluoroethanol and acetonitrile (v/v=1 : 1) resulted in generation of the long-lived photoexcited state, which is detected by nanosecond laser transient absorption measurements. The transient absorption maximum (λmax) of the 2E excited state of [(Bn-TPEN)MnIV(O)]2+−Sc(NO3)3 is observed at 620 nm with lifetimes of 7.1 μs. The λmax value is blue-shifted and the lifetime becomes longer as compared with the previously reported values of λmax (640 nm) and lifetime (6.4 μs) of the 2E excited state of the 1 : 2 complex between [(Bn-TPEN)MnIV(O)]2+ and Sc(OTf)3 ([(Bn-TPEN)MnIV(O)]2+−(Sc(OTf)3)2). The electron-transfer reactivity of the 2E excited states of [(Bn-TPEN)MnIV(O)]2+−Sc(NO3)3 was similar to that of [(Bn-TPEN)MnIV(O)]2+−(Sc(OTf)3)2. The long lifetime and the high reactivity of the 2E excited state of [(Bn-TPEN)MnIV(O)]2+−Sc(NO3)3 provide an excellent photooxidant for oxidation of compounds, which would otherwise be impossible to be oxidized.

Original languageEnglish
Pages (from-to)1049-1056
Number of pages8
JournalIsrael Journal of Chemistry
Volume60
Issue number10-11
DOIs
StatePublished - 1 Oct 2020

Bibliographical note

Funding Information:
This work was supported by NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N), GRL (NRF-2010-00353 to W.N.), Basic Science Research Program (2017R1D1A1B03029982 to Y.M.L. and 2017R1D1A1B03032615 to S.F.), and Grants-in-Aid (no. 16H02268 to S.F.) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT).

Funding Information:
This work was supported by NRF of Korea through CRI (NRF‐2012R1A3A2048842 to W.N), GRL (NRF‐2010‐00353 to W.N.), Basic Science Research Program (2017R1D1A1B03029982 to Y.M.L. and 2017R1D1A1B03032615 to S.F.), and Grants‐in‐Aid (no. 16H02268 to S.F.) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT).

Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

  • electron transfer
  • manganese(IV)-oxo complex
  • photoexcited state
  • scandium ion

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