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Updated: Jul 10, 2026

Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Magnetic interaction of tri- and di-oxytriphenylamine radical cation FeCl4 salts
Masato Kuratsu1, Shuichi Suzuki, Masatoshi Kozaki
1Department of Chemistry, Graduate School of Science, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan.
Abstract:
The tetrachloroferrates of the 2,2':6',2'':6'',6-trioxytriphenylamine (TOT.+.FeCl4-) and 2,2':6',2''-dioxytriphenylamine (DOT.+.FeCl4-) radical cations were prepared, and their structures, magnetic properties, and the relationship between them were investigated. The TOT.+ moiety had a highly planar structure and packed as a dimer surrounded by tetrachroferrates, which also formed a dimer structure. The magnetic properties of TOT.+.FeCl4- were characterized by strong (2J/kB=approximately -1.3x10(3) K, H=-2JS1/2.S1/2) and weak (2J/kB=-1.76 K, H=-2JS5/2.S5/2) antiferromagnetic interactions due to the (TOT.+)2 and (FeCl4-)2 structures, respectively. DOT.+ had a twisted form and no dimer formation was observed between the DOT.+'s and FeCl4-'s. Instead, short contacts between the DOT.+ and chlorine atoms and between the DOT.+'s producing a DOT.+ chain were observed. The magnetic properties of DOT.+.FeCl4- were characterized by a 3D magnetic phase transition to an antiferromagnet with TN=approximately 8 K.
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