Details
| Original language | English |
|---|---|
| Pages (from-to) | 7449-7452 |
| Number of pages | 4 |
| Journal | Chemistry - A European Journal |
| Volume | 25 |
| Issue number | 31 |
| Early online date | 28 Mar 2019 |
| Publication status | Published - 4 Jun 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.
Keywords
- cobalt, cyanides, hydrogen bonds, mixed-valent compounds, spin transition
ASJC Scopus subject areas
- Chemical Engineering(all)
- Catalysis
- Chemistry(all)
- Organic Chemistry
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In: Chemistry - A European Journal, Vol. 25, No. 31, 04.06.2019, p. 7449-7452.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
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.
KW - cobalt
KW - cyanides
KW - hydrogen bonds
KW - mixed-valent compounds
KW - spin transition
UR - http://www.scopus.com/inward/record.url?scp=85065024727&partnerID=8YFLogxK
U2 - 10.1002/chem.201901383
DO - 10.1002/chem.201901383
M3 - Article
C2 - 30920109
AN - SCOPUS:85065024727
VL - 25
SP - 7449
EP - 7452
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 31
ER -