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

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

doi:10.1002/chem.201901383

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

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

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

2 Citations (Scopus)

Abstract

A hydrogen-bonding donor–acceptor system, [Co₂Fe₂(bpy*)₄(CN)₆(tp*)₂](PF₆)₂⋅2ABA⋅4BN⋅2PE (1 s_olv), 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 s_olv 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 d_esolv, 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.

Original language	English
Pages (from-to)	7449-7452
Number of pages	4
Journal	Chemistry - A European Journal
Volume	25
Issue number	31
DOIs	https://doi.org/10.1002/chem.201901383
Publication status	Published - 2019 Jun 4
Externally published	Yes

Keywords

cobalt
cyanides
hydrogen bonds
mixed-valent compounds
spin transition

ASJC Scopus subject areas

Catalysis
Organic Chemistry

Access to Document

10.1002/chem.201901383

Cite this

Solid-State Hydrogen-Bond Alterations in a [Co₂Fe₂] Complex with Bifunctional Hydrogen-Bonding Donors. / Nihei, Masayuki; Yanai, Yuta; Natke, Dominik; Takayama, Ryo; Kato, Marina; Sekine, Yoshihiro; Renz, Franz; Oshio, Hiroki.

In: Chemistry - A European Journal, Vol. 25, No. 31, 04.06.2019, p. 7449-7452.

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

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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. Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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AU - Nihei, Masayuki

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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. Publisher Copyright: © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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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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