Molecular Insights into the Ligand-Based Six-Proton- and Six-Electron-Transfer Processes Between Tris-ortho-Phenylenediamines and Tris-ortho-Benzoquinodiimines

Takeshi Matsumoto; Risa Yamamoto; Masanori Wakizaka; Akinobu Nakada; Ho Chol Chang

doi:10.1002/chem.202001873

Molecular Insights into the Ligand-Based Six-Proton- and Six-Electron-Transfer Processes Between Tris-ortho-Phenylenediamines and Tris-ortho-Benzoquinodiimines

Takeshi Matsumoto, Risa Yamamoto, Masanori Wakizaka, Akinobu Nakada, Ho Chol Chang

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

1 Citation (Scopus)

Abstract

The global demand for energy and the concerns over climate issues renders the development of alternative renewable energy sources such as hydrogen (H₂) important. A high-spin (hs) Fe^II complex with o-phenylenediamine (opda) ligands, [Fe^II(opda)₃]²⁺ (hs-[6R]²⁺), was reported showing photochemical H₂ evolution. In addition, a low-spin (ls) [Fe^II(bqdi)₃]²⁺ (bqdi: o-benzoquinodiimine) (ls-[0R]²⁺) formation by O₂ oxidation of hs-[6R]²⁺, accompanied by ligand-based six-proton and six-electron transfer, revealed the potential of the complex with redox-active ligands as a novel multiple-proton and -electron storage material, albeit that the mechanism has not yet been understood. This paper reports that the oxidized ls-[0R][PF₆]₂ can be reduced by hydrazine giving ls-[Fe^II(opda)(bqdi)₂][PF₆]₂ (ls-[2R][PF₆]₂) and ls-[Fe^II(opda)₂(bqdi)][PF₆]₂ (ls-[4R][PF₆]₂) with localized ligand-based proton-coupled mixed-valence (LPMV) states. The first isolation and characterization of the key intermediates with LPMV states offer unprecedented molecular insights into the design of photoresponsive molecule-based hydrogen-storage materials.

Original language	English
Pages (from-to)	9609-9619
Number of pages	11
Journal	Chemistry - A European Journal
Volume	26
Issue number	43
DOIs	https://doi.org/10.1002/chem.202001873
Publication status	Published - 2020 Aug 3
Externally published	Yes

Keywords

iron
N ligands
oxidation
reduction
valency

ASJC Scopus subject areas

Catalysis
Organic Chemistry

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/chem.202001873

Cite this

Molecular Insights into the Ligand-Based Six-Proton- and Six-Electron-Transfer Processes Between Tris-ortho-Phenylenediamines and Tris-ortho-Benzoquinodiimines. / Matsumoto, Takeshi; Yamamoto, Risa; Wakizaka, Masanori; Nakada, Akinobu; Chang, Ho Chol.

In: Chemistry - A European Journal, Vol. 26, No. 43, 03.08.2020, p. 9609-9619.

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

@article{1d4cbdc29833431fb91e094b8abedda9,

title = "Molecular Insights into the Ligand-Based Six-Proton- and Six-Electron-Transfer Processes Between Tris-ortho-Phenylenediamines and Tris-ortho-Benzoquinodiimines",

abstract = "The global demand for energy and the concerns over climate issues renders the development of alternative renewable energy sources such as hydrogen (H2) important. A high-spin (hs) FeII complex with o-phenylenediamine (opda) ligands, [FeII(opda)3]2+ (hs-[6R]2+), was reported showing photochemical H2 evolution. In addition, a low-spin (ls) [FeII(bqdi)3]2+ (bqdi: o-benzoquinodiimine) (ls-[0R]2+) formation by O2 oxidation of hs-[6R]2+, accompanied by ligand-based six-proton and six-electron transfer, revealed the potential of the complex with redox-active ligands as a novel multiple-proton and -electron storage material, albeit that the mechanism has not yet been understood. This paper reports that the oxidized ls-[0R][PF6]2 can be reduced by hydrazine giving ls-[FeII(opda)(bqdi)2][PF6]2 (ls-[2R][PF6]2) and ls-[FeII(opda)2(bqdi)][PF6]2 (ls-[4R][PF6]2) with localized ligand-based proton-coupled mixed-valence (LPMV) states. The first isolation and characterization of the key intermediates with LPMV states offer unprecedented molecular insights into the design of photoresponsive molecule-based hydrogen-storage materials.",

keywords = "iron, N ligands, oxidation, reduction, valency",

author = "Takeshi Matsumoto and Risa Yamamoto and Masanori Wakizaka and Akinobu Nakada and Chang, {Ho Chol}",

note = "Funding Information: The authors are grateful to Prof. H. Miyasaka and Dr. W. Kosaka (Tohoku Univ.), Prof. T. Hiyama and Dr. Y. Minami (Chuo Univ.) for their support with the crystallographic measurements, as well as to Prof. Y. Ishii, Dr. S. Kodama, and Dr. T. Kuwabara (Chuo Univ.) for their support with elemental analyses. This work was financially supported by: the Japan Society for the Promotion of Science (JSPS) via KAKENHI grants JP19H02736, JP18K19101, JP17H04871, and JP16H04123; the Ministry of Education, Culture, Sports, Science and Technology (MEXT) via KAKENHI grants JP19H04593 (Coordination Asymmetry) and JP18H05517 (Hydrogenomics); the JST via PRESTO grant JPMJPR16SA; the Research Promotion Fund from the Promotion and Mutual Aid Corporation for Private Schools of Japan; the Inter‐university Cooperative Research Program of the Institute for Materials Research, Tohoku University (Proposal 17K0091). Publisher Copyright: {\textcopyright} 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2020",

month = aug,

day = "3",

doi = "10.1002/chem.202001873",

language = "English",

volume = "26",

pages = "9609--9619",

journal = "Chemistry - A European Journal",

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T1 - Molecular Insights into the Ligand-Based Six-Proton- and Six-Electron-Transfer Processes Between Tris-ortho-Phenylenediamines and Tris-ortho-Benzoquinodiimines

AU - Matsumoto, Takeshi

AU - Yamamoto, Risa

AU - Wakizaka, Masanori

AU - Nakada, Akinobu

AU - Chang, Ho Chol

N1 - Funding Information: The authors are grateful to Prof. H. Miyasaka and Dr. W. Kosaka (Tohoku Univ.), Prof. T. Hiyama and Dr. Y. Minami (Chuo Univ.) for their support with the crystallographic measurements, as well as to Prof. Y. Ishii, Dr. S. Kodama, and Dr. T. Kuwabara (Chuo Univ.) for their support with elemental analyses. This work was financially supported by: the Japan Society for the Promotion of Science (JSPS) via KAKENHI grants JP19H02736, JP18K19101, JP17H04871, and JP16H04123; the Ministry of Education, Culture, Sports, Science and Technology (MEXT) via KAKENHI grants JP19H04593 (Coordination Asymmetry) and JP18H05517 (Hydrogenomics); the JST via PRESTO grant JPMJPR16SA; the Research Promotion Fund from the Promotion and Mutual Aid Corporation for Private Schools of Japan; the Inter‐university Cooperative Research Program of the Institute for Materials Research, Tohoku University (Proposal 17K0091). Publisher Copyright: © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2020/8/3

Y1 - 2020/8/3

N2 - The global demand for energy and the concerns over climate issues renders the development of alternative renewable energy sources such as hydrogen (H2) important. A high-spin (hs) FeII complex with o-phenylenediamine (opda) ligands, [FeII(opda)3]2+ (hs-[6R]2+), was reported showing photochemical H2 evolution. In addition, a low-spin (ls) [FeII(bqdi)3]2+ (bqdi: o-benzoquinodiimine) (ls-[0R]2+) formation by O2 oxidation of hs-[6R]2+, accompanied by ligand-based six-proton and six-electron transfer, revealed the potential of the complex with redox-active ligands as a novel multiple-proton and -electron storage material, albeit that the mechanism has not yet been understood. This paper reports that the oxidized ls-[0R][PF6]2 can be reduced by hydrazine giving ls-[FeII(opda)(bqdi)2][PF6]2 (ls-[2R][PF6]2) and ls-[FeII(opda)2(bqdi)][PF6]2 (ls-[4R][PF6]2) with localized ligand-based proton-coupled mixed-valence (LPMV) states. The first isolation and characterization of the key intermediates with LPMV states offer unprecedented molecular insights into the design of photoresponsive molecule-based hydrogen-storage materials.

AB - The global demand for energy and the concerns over climate issues renders the development of alternative renewable energy sources such as hydrogen (H2) important. A high-spin (hs) FeII complex with o-phenylenediamine (opda) ligands, [FeII(opda)3]2+ (hs-[6R]2+), was reported showing photochemical H2 evolution. In addition, a low-spin (ls) [FeII(bqdi)3]2+ (bqdi: o-benzoquinodiimine) (ls-[0R]2+) formation by O2 oxidation of hs-[6R]2+, accompanied by ligand-based six-proton and six-electron transfer, revealed the potential of the complex with redox-active ligands as a novel multiple-proton and -electron storage material, albeit that the mechanism has not yet been understood. This paper reports that the oxidized ls-[0R][PF6]2 can be reduced by hydrazine giving ls-[FeII(opda)(bqdi)2][PF6]2 (ls-[2R][PF6]2) and ls-[FeII(opda)2(bqdi)][PF6]2 (ls-[4R][PF6]2) with localized ligand-based proton-coupled mixed-valence (LPMV) states. The first isolation and characterization of the key intermediates with LPMV states offer unprecedented molecular insights into the design of photoresponsive molecule-based hydrogen-storage materials.

KW - iron

KW - N ligands

KW - oxidation

KW - reduction

KW - valency

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DO - 10.1002/chem.202001873

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AN - SCOPUS:85087613095

VL - 26

SP - 9609

EP - 9619

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

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ER -

Molecular Insights into the Ligand-Based Six-Proton- and Six-Electron-Transfer Processes Between Tris-ortho-Phenylenediamines and Tris-ortho-Benzoquinodiimines

Abstract

Keywords

ASJC Scopus subject areas

UN SDGs

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