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Solid‐State Hydrogen‐Bond Alterations in a [Co 2 Fe 2 ] Complex with Bifunctional Hydrogen‐Bonding Donors
Author(s) -
Nihei Masayuki,
Yanai Yuta,
Natke Dominik,
Takayama Ryo,
Kato Marina,
Sekine Yoshihiro,
Renz Franz,
Oshio Hiroki
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201901383
Subject(s) - bifunctional , hydrogen bond , solid state , hydrogen , low barrier hydrogen bond , chemistry , materials science , crystallography , molecule , organic chemistry , catalysis
A hydrogen‐bonding donor–acceptor system, [Co 2 Fe 2 (bpy*) 4 (CN) 6 (tp*) 2 ](PF 6 ) 2 ⋅2ABA⋅4BN⋅2PE ( 1 s olv ), was prepared by co‐crystallization of an external stimuli‐responsive cyanide‐bridged tetranuclear [Co 2 Fe 2 ] 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 [Co 2 Fe 2 ] 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 [Co 2 Fe 2 ] complex shows solid‐state modulations of hydrogen‐bond strengths by external stimuli.