Solid State Characterization of One‐ and Two‐Electron Oxidized Cu<sup>II</sup>‐salen Complexes with <i>para</i>‐Substituents: Geometric Structure‐Magnetic Property Relationship
Tomoyuki Takeyama, Takashi Suzuki, Misa Kikuchi, Misato Kobayashi, Hiromi Oshita, Kyohei Kawashima, Seiji Mori, Hitoshi Abe, Norihisa Hoshino, Satoshi Iwatsuki, Yuichi Shimazaki
Abstract
Abstract 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)]SbCl 6 revealed the intermolecular π‐π stacking interaction of the two phenolate moieties with those of the neighboring complex cations to form the one‐dimensional chain. Such a π‐π stacking interaction could not be detected in the two‐electron oxidized complex [Cu(MeS‐salen)](SbCl 6 ) 2 and the oxidized methoxy‐substituted complexes [Cu(MeO‐salen)](SbF 6 ) n ( n =1, 2). Magnetic study of [Cu(MeO‐salen)]SbF 6 showed a weak antiferromagnetic interaction between the Cu II ion and phenoxyl radical unpaired electron spins, while [Cu(MeS‐salen)]SbCl 6 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.