A Brønsted-Ligand-Based Iron Complex as a Molecular Switch with Five Accessible States

Publikation: Beitrag in FachzeitschriftArtikelForschungPeer-Review

Autoren

  • Takuya Shiga
  • Ryo Saiki
  • Lisa Akiyama
  • Reiji Kumai
  • Dominik Natke
  • Franz Renz
  • Jamie M. Cameron
  • Graham N. Newton
  • Hiroki Oshio

Organisationseinheiten

Externe Organisationen

  • University of Tsukuba
  • High Energy Accelerator Research Organization (KEK)
  • University of Nottingham
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Details

OriginalspracheEnglisch
Seiten (von - bis)5658-5662
Seitenumfang5
FachzeitschriftAngewandte Chemie
Jahrgang58
Ausgabenummer17
Frühes Online-Datum12 Feb. 2019
PublikationsstatusVeröffentlicht - 9 Apr. 2019

Abstract

A mononuclear Fe II complex, prepared with a Brønsted diacid ligand, H 2 L (H 2 L=2-[5-phenyl-1H-pyrazole-3-yl] 6-benzimidazole pyridine), shows switchable physical properties and was isolated in five different electronic states. The spin crossover (SCO) complex, [Fe II (H 2 L) 2 ](BF 4 ) 2 (1 A ), exhibits abrupt spin transition at T 1/2 =258 K, and treatment with base yields a deprotonated analogue [Fe II (HL) 2 ] (1 B ), which shows gradual SCO above 350 K. A range of Fe III analogues were also characterized. [Fe III (HL)(H 2 L)](BF 4 )Cl (1 C ) has an S=5/2 spin state, while the deprotonated complexes [Fe III (L)(HL)], (1 D ), and (TEA)[Fe III (L) 2 ], (1 E ) exist in the low-spin S=1/2 state. The electronic properties of the five complexes were fully characterized and we demonstrate in situ switching between multiple states in both solution and the solid-state. The versatility of this simple mononuclear system illustrates how proton donor/acceptor ligands can vastly increase the range of accessible states in switchable molecular devices.

ASJC Scopus Sachgebiete

Zitieren

A Brønsted-Ligand-Based Iron Complex as a Molecular Switch with Five Accessible States. / Shiga, Takuya; Saiki, Ryo; Akiyama, Lisa et al.
in: Angewandte Chemie , Jahrgang 58, Nr. 17, 09.04.2019, S. 5658-5662.

Publikation: Beitrag in FachzeitschriftArtikelForschungPeer-Review

Shiga, T, Saiki, R, Akiyama, L, Kumai, R, Natke, D, Renz, F, Cameron, JM, Newton, GN & Oshio, H 2019, 'A Brønsted-Ligand-Based Iron Complex as a Molecular Switch with Five Accessible States', Angewandte Chemie , Jg. 58, Nr. 17, S. 5658-5662. https://doi.org/10.1002/anie.201900909
Shiga, T., Saiki, R., Akiyama, L., Kumai, R., Natke, D., Renz, F., Cameron, J. M., Newton, G. N., & Oshio, H. (2019). A Brønsted-Ligand-Based Iron Complex as a Molecular Switch with Five Accessible States. Angewandte Chemie , 58(17), 5658-5662. https://doi.org/10.1002/anie.201900909
Shiga T, Saiki R, Akiyama L, Kumai R, Natke D, Renz F et al. A Brønsted-Ligand-Based Iron Complex as a Molecular Switch with Five Accessible States. Angewandte Chemie . 2019 Apr 9;58(17):5658-5662. Epub 2019 Feb 12. doi: 10.1002/anie.201900909
Shiga, Takuya ; Saiki, Ryo ; Akiyama, Lisa et al. / A Brønsted-Ligand-Based Iron Complex as a Molecular Switch with Five Accessible States. in: Angewandte Chemie . 2019 ; Jahrgang 58, Nr. 17. S. 5658-5662.
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title = "A Br{\o}nsted-Ligand-Based Iron Complex as a Molecular Switch with Five Accessible States",
abstract = " A mononuclear Fe II complex, prepared with a Br{\o}nsted diacid ligand, H 2 L (H 2 L=2-[5-phenyl-1H-pyrazole-3-yl] 6-benzimidazole pyridine), shows switchable physical properties and was isolated in five different electronic states. The spin crossover (SCO) complex, [Fe II (H 2 L) 2 ](BF 4 ) 2 (1 A ), exhibits abrupt spin transition at T 1/2 =258 K, and treatment with base yields a deprotonated analogue [Fe II (HL) 2 ] (1 B ), which shows gradual SCO above 350 K. A range of Fe III analogues were also characterized. [Fe III (HL)(H 2 L)](BF 4 )Cl (1 C ) has an S=5/2 spin state, while the deprotonated complexes [Fe III (L)(HL)], (1 D ), and (TEA)[Fe III (L) 2 ], (1 E ) exist in the low-spin S=1/2 state. The electronic properties of the five complexes were fully characterized and we demonstrate in situ switching between multiple states in both solution and the solid-state. The versatility of this simple mononuclear system illustrates how proton donor/acceptor ligands can vastly increase the range of accessible states in switchable molecular devices. ",
keywords = "Br{\o}nsted acid/base, iron, magnetism, molecular switch, spin crossover",
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note = "Funding information: This work was supported by a Grant-in-Aid for Challenging Exploratory Research (no. 18K19088), Grant-in-Aid for Scientific Research (C) (no. 17K05800) and Grant-in-Aid for Scientific Research on Innovative Areas “Coordination Asymmetry” (no. JP16H06523) from the Japan Society for the Promotion of Science (JSPS). This work was performed under the approval of the Photon Factory Program Advisory Committee (Proposal No. 2018G102). We thank the University of Nottingham Propulsion Futures Beacon and the Leverhulme Trust (RPG-2016-442) for funding towards this research.",
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TY - JOUR

T1 - A Brønsted-Ligand-Based Iron Complex as a Molecular Switch with Five Accessible States

AU - Shiga, Takuya

AU - Saiki, Ryo

AU - Akiyama, Lisa

AU - Kumai, Reiji

AU - Natke, Dominik

AU - Renz, Franz

AU - Cameron, Jamie M.

AU - Newton, Graham N.

AU - Oshio, Hiroki

N1 - Funding information: This work was supported by a Grant-in-Aid for Challenging Exploratory Research (no. 18K19088), Grant-in-Aid for Scientific Research (C) (no. 17K05800) and Grant-in-Aid for Scientific Research on Innovative Areas “Coordination Asymmetry” (no. JP16H06523) from the Japan Society for the Promotion of Science (JSPS). This work was performed under the approval of the Photon Factory Program Advisory Committee (Proposal No. 2018G102). We thank the University of Nottingham Propulsion Futures Beacon and the Leverhulme Trust (RPG-2016-442) for funding towards this research.

PY - 2019/4/9

Y1 - 2019/4/9

N2 - A mononuclear Fe II complex, prepared with a Brønsted diacid ligand, H 2 L (H 2 L=2-[5-phenyl-1H-pyrazole-3-yl] 6-benzimidazole pyridine), shows switchable physical properties and was isolated in five different electronic states. The spin crossover (SCO) complex, [Fe II (H 2 L) 2 ](BF 4 ) 2 (1 A ), exhibits abrupt spin transition at T 1/2 =258 K, and treatment with base yields a deprotonated analogue [Fe II (HL) 2 ] (1 B ), which shows gradual SCO above 350 K. A range of Fe III analogues were also characterized. [Fe III (HL)(H 2 L)](BF 4 )Cl (1 C ) has an S=5/2 spin state, while the deprotonated complexes [Fe III (L)(HL)], (1 D ), and (TEA)[Fe III (L) 2 ], (1 E ) exist in the low-spin S=1/2 state. The electronic properties of the five complexes were fully characterized and we demonstrate in situ switching between multiple states in both solution and the solid-state. The versatility of this simple mononuclear system illustrates how proton donor/acceptor ligands can vastly increase the range of accessible states in switchable molecular devices.

AB - A mononuclear Fe II complex, prepared with a Brønsted diacid ligand, H 2 L (H 2 L=2-[5-phenyl-1H-pyrazole-3-yl] 6-benzimidazole pyridine), shows switchable physical properties and was isolated in five different electronic states. The spin crossover (SCO) complex, [Fe II (H 2 L) 2 ](BF 4 ) 2 (1 A ), exhibits abrupt spin transition at T 1/2 =258 K, and treatment with base yields a deprotonated analogue [Fe II (HL) 2 ] (1 B ), which shows gradual SCO above 350 K. A range of Fe III analogues were also characterized. [Fe III (HL)(H 2 L)](BF 4 )Cl (1 C ) has an S=5/2 spin state, while the deprotonated complexes [Fe III (L)(HL)], (1 D ), and (TEA)[Fe III (L) 2 ], (1 E ) exist in the low-spin S=1/2 state. The electronic properties of the five complexes were fully characterized and we demonstrate in situ switching between multiple states in both solution and the solid-state. The versatility of this simple mononuclear system illustrates how proton donor/acceptor ligands can vastly increase the range of accessible states in switchable molecular devices.

KW - Brønsted acid/base

KW - iron

KW - magnetism

KW - molecular switch

KW - spin crossover

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VL - 58

SP - 5658

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JO - Angewandte Chemie

JF - Angewandte Chemie

SN - 1433-7851

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