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

1 Citation (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

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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",

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AU - Takayama, Ryo

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AU - Renz, Franz

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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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