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

doi:10.1002/ijch.201900147

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

Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

Photoexcitation of a manganese(IV)-oxo-scandium nitrate complex ([(Bn-TPEN)Mn^IV(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 (λ_max) of the ²E excited state of [(Bn-TPEN)Mn^IV(O)]²⁺−Sc(NO₃)₃ is observed at 620 nm with lifetimes of 7.1 μs. The λ_max value is blue-shifted and the lifetime becomes longer as compared with the previously reported values of λ_max (640 nm) and lifetime (6.4 μs) of the ²E excited state of the 1 : 2 complex between [(Bn-TPEN)Mn^IV(O)]²⁺ and Sc(OTf)₃ ([(Bn-TPEN)Mn^IV(O)]²⁺−(Sc(OTf)₃)₂). The electron-transfer reactivity of the ²E excited states of [(Bn-TPEN)Mn^IV(O)]²⁺−Sc(NO₃)₃ was similar to that of [(Bn-TPEN)Mn^IV(O)]²⁺−(Sc(OTf)₃)₂. The long lifetime and the high reactivity of the ²E excited state of [(Bn-TPEN)Mn^IV(O)]²⁺−Sc(NO₃)₃ provide an excellent photooxidant for oxidation of compounds, which would otherwise be impossible to be oxidized.

Original language	English
Pages (from-to)	1049-1056
Number of pages	8
Journal	Israel Journal of Chemistry
Volume	60
Issue number	10-11
DOIs	https://doi.org/10.1002/ijch.201900147
State	Published - 1 Oct 2020

Keywords

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

Access to Document

10.1002/ijch.201900147

Cite this

@article{b14973fb30a44aa5a626f349ca68bce7,

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

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.",

keywords = "electron transfer, manganese(IV)-oxo complex, photoexcited state, scandium ion",

author = "Namita Sharma and Lee, {Yong Min} and Wonwoo Nam and Shunichi Fukuzumi",

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: {\textcopyright} 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2020",

month = oct,

day = "1",

doi = "10.1002/ijch.201900147",

language = "English",

volume = "60",

pages = "1049--1056",

journal = "Israel Journal of Chemistry",

issn = "0021-2148",

publisher = "Wiley-Blackwell",

number = "10-11",

}

TY - JOUR

T1 - Generation and Electron-Transfer Reactivity of the Long-Lived Photoexcited State of a Manganese(IV)-Oxo-Scandium Nitrate Complex

AU - Sharma, Namita

AU - Lee, Yong Min

AU - Nam, Wonwoo

AU - Fukuzumi, Shunichi

N1 - 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

PY - 2020/10/1

Y1 - 2020/10/1

N2 - 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.

AB - 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.

KW - electron transfer

KW - manganese(IV)-oxo complex

KW - photoexcited state

KW - scandium ion

UR - http://www.scopus.com/inward/record.url?scp=85078819800&partnerID=8YFLogxK

U2 - 10.1002/ijch.201900147

DO - 10.1002/ijch.201900147

M3 - Article

AN - SCOPUS:85078819800

SN - 0021-2148

VL - 60

SP - 1049

EP - 1056

JO - Israel Journal of Chemistry

JF - Israel Journal of Chemistry

IS - 10-11

ER -

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

Abstract

Keywords

Access to Document

Fingerprint

Cite this