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
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
UR - http://www.scopus.com/inward/citedby.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 -