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

被引：26
|
作者：
Nihei, Masayuki [1 ]
Yanai, Yuta [1 ]
Natke, Dominik [2 ]
Takayama, Ryo [1 ]
Kato, Marina [1 ]
Sekine, Yoshihiro [1 ]
Renz, Franz [2 ]
Oshio, Hiroki [1 ]
机构：
[1] Univ Tsukuba, Fac Pure & Appl Sci, Dept Chem, Tennodai 1-1-1, Tsukuba, Ibaraki, Japan
[2] Leibniz Univ Hannover, Inst Anorgan Chem, Callinstr 9, D-30167 Hannover, Germany
来源：
CHEMISTRY-A EUROPEAN JOURNAL | 2019年 / 25卷 / 31期
关键词：
cobalt; cyanides; hydrogen bonds; mixed-valent compounds; spin transition; INTRAMOLECULAR ELECTRON-TRANSFER; METAL CHARGE-TRANSFER; SPIN TRANSITION; REDOX; MAGNETISM; CRYSTALS; SPECTRA;
D O I：
10.1002/chem.201901383
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
A hydrogen-bonding donor-acceptor system, [Co2Fe2(bpy*)(4)(CN)(6)(tp*)(2)](PF6)(2)center dot 2ABA center dot 4BN center dot 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.
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页码：7449 / 7452
页数：4
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