Solid-State Hydrogen-Bond Alterations in a [Co2Fe2] Complex with Bifunctional Hydrogen-Bonding Donors

Publikation: Beitrag in Fachzeitschrift › Artikel › Forschung › Peer-Review

Autoren

  • Masayuki Nihei
  • Yuta Yanai
  • Dominik Natke
  • Ryo Takayama
  • Marina Kato
  • Yoshihiro Sekine
  • Franz Renz
  • Hiroki Oshio

Organisationseinheiten

Externe Organisationen

  • University of Tsukuba
Forschungs-netzwerk anzeigen

Details

OriginalspracheEnglisch
Seiten (von - bis)7449-7452
Seitenumfang4
FachzeitschriftChemistry - A European Journal
Jahrgang25
Ausgabenummer31
Frühes Online-Datum28 März 2019
PublikationsstatusVeröffentlicht - 4 Juni 2019

Abstract

A hydrogen-bonding donor–acceptor system, [Co2Fe2(bpy*)4(CN)6(tp*)2](PF6)2⋅2ABA⋅4BN⋅2PE (1 solv), was prepared by co-crystallization of an external stimuli-responsive cyanide-bridged tetranuclear [Co2Fe2] complex and bifunctional hydrogen-bonding donors, p-aminobenzoic acid. Compound 1 solv exhibited a gradual electron-transfer-coupled spin transition (ETCST), and the removal of solvent molecules led to an abrupt thermal ETCST behavior with increased transition temperature. X-ray structural analysis revealed that the modification of ETCST was caused by a significant alteration of a hydrogen-bonding mode between the tetranuclear [Co2Fe2]2+ cations and ABA molecules. Variable temperature IR measurements indicated that the desolvated form, 1 desolv, showed dynamic alteration of hydrogen-bonding interactions coupled with thermal ETCST behavior. These results suggested that the tetranuclear [Co2Fe2] complex shows solid-state modulations of hydrogen-bond strengths by external stimuli.

ASJC Scopus Sachgebiete

Zitieren

Solid-State Hydrogen-Bond Alterations in a [Co2Fe2] Complex with Bifunctional Hydrogen-Bonding Donors. / Nihei, Masayuki; Yanai, Yuta; Natke, Dominik et al.
in: Chemistry - A European Journal, Jahrgang 25, Nr. 31, 04.06.2019, S. 7449-7452.

Publikation: Beitrag in Fachzeitschrift › Artikel › Forschung › Peer-Review

Nihei, M, Yanai, Y, Natke, D, Takayama, R, Kato, M, Sekine, Y, Renz, F & Oshio, H 2019, 'Solid-State Hydrogen-Bond Alterations in a [Co2Fe2] Complex with Bifunctional Hydrogen-Bonding Donors', Chemistry - A European Journal, Jg. 25, Nr. 31, S. 7449-7452. https://doi.org/10.1002/chem.201901383
Nihei, M., Yanai, Y., Natke, D., Takayama, R., Kato, M., Sekine, Y., Renz, F., & Oshio, H. (2019). Solid-State Hydrogen-Bond Alterations in a [Co2Fe2] Complex with Bifunctional Hydrogen-Bonding Donors. Chemistry - A European Journal, 25(31), 7449-7452. https://doi.org/10.1002/chem.201901383
Nihei M, Yanai Y, Natke D, Takayama R, Kato M, Sekine Y et al. Solid-State Hydrogen-Bond Alterations in a [Co2Fe2] Complex with Bifunctional Hydrogen-Bonding Donors. Chemistry - A European Journal. 2019 Jun 4;25(31):7449-7452. Epub 2019 Mär 28. doi: 10.1002/chem.201901383
Nihei, Masayuki ; Yanai, Yuta ; Natke, Dominik et al. / Solid-State Hydrogen-Bond Alterations in a [Co2Fe2] Complex with Bifunctional Hydrogen-Bonding Donors. in: Chemistry - A European Journal. 2019 ; Jahrgang 25, Nr. 31. S. 7449-7452.
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title = "Solid-State Hydrogen-Bond Alterations in a [Co2Fe2] Complex with Bifunctional Hydrogen-Bonding Donors",
abstract = "A hydrogen-bonding donor–acceptor system, [Co2Fe2(bpy*)4(CN)6(tp*)2](PF6)2⋅2ABA⋅4BN⋅2PE (1 solv), was prepared by co-crystallization of an external stimuli-responsive cyanide-bridged tetranuclear [Co2Fe2] complex and bifunctional hydrogen-bonding donors, p-aminobenzoic acid. Compound 1 solv exhibited a gradual electron-transfer-coupled spin transition (ETCST), and the removal of solvent molecules led to an abrupt thermal ETCST behavior with increased transition temperature. X-ray structural analysis revealed that the modification of ETCST was caused by a significant alteration of a hydrogen-bonding mode between the tetranuclear [Co2Fe2]2+ cations and ABA molecules. Variable temperature IR measurements indicated that the desolvated form, 1 desolv, showed dynamic alteration of hydrogen-bonding interactions coupled with thermal ETCST behavior. These results suggested that the tetranuclear [Co2Fe2] complex shows solid-state modulations of hydrogen-bond strengths by external stimuli.",
keywords = "cobalt, cyanides, hydrogen bonds, mixed-valent compounds, spin transition",
author = "Masayuki Nihei and Yuta Yanai and Dominik Natke and Ryo Takayama and Marina Kato and Yoshihiro Sekine and Franz Renz and Hiroki Oshio",
note = "Funding information: This work was supported by a JSPS KAKENHI Grant Number 26288021, 18H01989, and 16H06523 (Coordination Asymmetry). D.N. and F.R. would like to thank the German Academic Exchange Service (DAAD) and Hannover School for Nanotechnology (HSN) for funding.",
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T1 - Solid-State Hydrogen-Bond Alterations in a [Co2Fe2] Complex with Bifunctional Hydrogen-Bonding Donors

AU - Nihei, Masayuki

AU - Yanai, Yuta

AU - Natke, Dominik

AU - Takayama, Ryo

AU - Kato, Marina

AU - Sekine, Yoshihiro

AU - Renz, Franz

AU - Oshio, Hiroki

N1 - Funding information: This work was supported by a JSPS KAKENHI Grant Number 26288021, 18H01989, and 16H06523 (Coordination Asymmetry). D.N. and F.R. would like to thank the German Academic Exchange Service (DAAD) and Hannover School for Nanotechnology (HSN) for funding.

PY - 2019/6/4

Y1 - 2019/6/4

N2 - A hydrogen-bonding donor–acceptor system, [Co2Fe2(bpy*)4(CN)6(tp*)2](PF6)2⋅2ABA⋅4BN⋅2PE (1 solv), was prepared by co-crystallization of an external stimuli-responsive cyanide-bridged tetranuclear [Co2Fe2] complex and bifunctional hydrogen-bonding donors, p-aminobenzoic acid. Compound 1 solv exhibited a gradual electron-transfer-coupled spin transition (ETCST), and the removal of solvent molecules led to an abrupt thermal ETCST behavior with increased transition temperature. X-ray structural analysis revealed that the modification of ETCST was caused by a significant alteration of a hydrogen-bonding mode between the tetranuclear [Co2Fe2]2+ cations and ABA molecules. Variable temperature IR measurements indicated that the desolvated form, 1 desolv, showed dynamic alteration of hydrogen-bonding interactions coupled with thermal ETCST behavior. These results suggested that the tetranuclear [Co2Fe2] complex shows solid-state modulations of hydrogen-bond strengths by external stimuli.

AB - A hydrogen-bonding donor–acceptor system, [Co2Fe2(bpy*)4(CN)6(tp*)2](PF6)2⋅2ABA⋅4BN⋅2PE (1 solv), was prepared by co-crystallization of an external stimuli-responsive cyanide-bridged tetranuclear [Co2Fe2] complex and bifunctional hydrogen-bonding donors, p-aminobenzoic acid. Compound 1 solv exhibited a gradual electron-transfer-coupled spin transition (ETCST), and the removal of solvent molecules led to an abrupt thermal ETCST behavior with increased transition temperature. X-ray structural analysis revealed that the modification of ETCST was caused by a significant alteration of a hydrogen-bonding mode between the tetranuclear [Co2Fe2]2+ cations and ABA molecules. Variable temperature IR measurements indicated that the desolvated form, 1 desolv, showed dynamic alteration of hydrogen-bonding interactions coupled with thermal ETCST behavior. These results suggested that the tetranuclear [Co2Fe2] complex shows solid-state modulations of hydrogen-bond strengths by external stimuli.

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KW - cyanides

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KW - spin transition

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