TY - JOUR
T1 - Solid State Characterization of One- and Two-Electron Oxidized CuII-salen Complexes with para-Substituents
T2 - Geometric Structure-Magnetic Property Relationship
AU - Takeyama, Tomoyuki
AU - Suzuki, Takashi
AU - Kikuchi, Misa
AU - Kobayashi, Misato
AU - Oshita, Hiromi
AU - Kawashima, Kyohei
AU - Mori, Seiji
AU - Abe, Hitoshi
AU - Hoshino, Norihisa
AU - Iwatsuki, Satoshi
AU - Shimazaki, Yuichi
N1 - Funding Information:
We would like to acknowledge Prof. Dr. Fumito Tani at Institute for Materials Chemistry and Engineering, Kyushu University for useful and helpful comments and discussion. This work was supported in part by Grants‐in‐Aid for Scientific Research (Nos. 25410060 and 16 K05716 to Y. S., Nos. 15 K05551 and 18 K05187 to S. I., and No. 21 K05016 to S. M.) from the Ministry of Education, Culture, Sports, Science, and Technology of Japan, Cooperative Research Program of “Network Joint Research Center for Materials and Devices” (Institute for Materials Chemistry and Engineering, Kyushu University). This work was also supported in part by a grant from Hyogo Science and Technology Association (to S. I.). The XAFS measurements were carried out under the approval of PF‐PAC No. 2016T003 to H.O. The generous allotment of computational time from the Research Center for Computational Science, the National Institute of Natural Science, Japan Is also gratefully acknowledged.
Funding Information:
We would like to acknowledge Prof. Dr. Fumito Tani at Institute for Materials Chemistry and Engineering, Kyushu University for useful and helpful comments and discussion. This work was supported in part by Grants-in-Aid for Scientific Researchy (Nos. 25410060 and 16 K05716 to Y.S., Nos. 15K05551 and 18 K05187 to S.I., and No. 21 K05016 to S.M.) from the Ministry of Education, Culture, Sports, Science, and Technology of Japan, Cooperative Research Program of “Network Joint Research Center for Materials and Devices” (Institute for Materials Chemistry and Engineering, Kyushu University). This work was also supported in part by a grant from Hyogo Science and Technology Association (to S.I.). The XAFS measurements were carried out under the approval of PF-PAC No. 2016T003 to H.O. The generous allotment of computational time from the Research Center for Computational Science, the National Institute of Natural Science, Japan is also gratefully acknowledged.
Publisher Copyright:
© 2021 Wiley-VCH GmbH
PY - 2021/10/21
Y1 - 2021/10/21
N2 - One- and two-electron oxidized CuII 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 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)](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 CuII 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.
AB - One- and two-electron oxidized CuII 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 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)](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 CuII 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.
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U2 - 10.1002/ejic.202100776
DO - 10.1002/ejic.202100776
M3 - Article
AN - SCOPUS:85116322290
SN - 1434-1948
VL - 2021
SP - 4133
EP - 4145
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 39
ER -