Solid State Characterization of One- and Two-Electron Oxidized Cu-II-salen Complexes with para-Substituents: Geometric Structure-Magnetic Property Relationship

One- and two-electron oxidized Cu-II complexes of Schiff base ligands with para-substituted phenolate moieties were synthesized and characterized. The crystal structure of the one-electron oxidized methylthio-substituted complex [Cu(MeS-salen)]SbCl6 revealed the intermolecular pi-pi stacking interac...

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Published inEuropean journal of inorganic chemistry Vol. 2021; no. 39; pp. 4133 - 4145
Main Authors Takeyama, Tomoyuki, Suzuki, Takashi, Kikuchi, Misa, Kobayashi, Misato, Oshita, Hiromi, Kawashima, Kyohei, Mori, Seiji, Abe, Hitoshi, Hoshino, Norihisa, Iwatsuki, Satoshi, Shimazaki, Yuichi
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 21.10.2021
Subjects
Chemistry
Chemistry, Inorganic & Nuclear
Physical Sciences
Science & Technology
Magnetic property
RADICAL STABILITY
TRANSITION-METAL-COMPLEXES
ACTIVE-SITE
PHASE-TRANSITIONS
CRYSTAL-STRUCTURE
Stacking interactions
Phenoxyl radical
GALACTOSE-OXIDASE
COPPER(II) COMPLEXES
EFFECTIVE EXCHANGE INTEGRALS
Oxidation
BASIS-SETS
Copper
ELECTRONIC-STRUCTURE
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Summary:One- and two-electron oxidized Cu-II complexes of Schiff base ligands with para-substituted phenolate moieties were synthesized and characterized. The crystal structure of the one-electron oxidized methylthio-substituted complex [Cu(MeS-salen)]SbCl6 revealed the intermolecular pi-pi stacking interaction of the two phenolate moieties with those of the neighboring complex cations to form the one-dimensional chain. Such a pi-pi stacking interaction could not be detected in the two-electron oxidized complex [Cu(MeS-salen)](SbCl6)(2) and the oxidized methoxy-substituted complexes [Cu(MeO-salen)](SbF6)(n) (n=1, 2). Magnetic study of [Cu(MeO-salen)]SbF6 showed a weak antiferromagnetic interaction between the Cu-II ion and phenoxyl radical unpaired electron spins, while [Cu(MeS-salen)]SbCl6 showed a ferromagnetism. Both of the two-electron oxidized complexes exhibited a relatively strong magnetic interaction between the two radical electrons, while the signs of the electron spins are different.
ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.202100776