1. Solid‐State Hydrogen‐Bond Alterations in a [Co 2 Fe 2 ] Complex with Bifunctional Hydrogen‐Bonding Donors
- Author
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Franz Renz, Yoshihiro Sekine, Dominik Natke, Yuta Yanai, Masayuki Nihei, Hiroki Oshio, Ryo Takayama, and Marina Kato
- Subjects
Hydrogen bond ,Transition temperature ,Organic Chemistry ,Solid-state ,Spin transition ,chemistry.chemical_element ,General Chemistry ,Catalysis ,Solvent ,Crystallography ,chemistry.chemical_compound ,chemistry ,Molecule ,Bifunctional ,Cobalt - Abstract
A hydrogen-bonding donor-acceptor system, [Co2 Fe2 (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 [Co2 Fe2 ] 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 [Co2 Fe2 ]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 [Co2 Fe2 ] complex shows solid-state modulations of hydrogen-bond strengths by external stimuli.
- Published
- 2019