Synthesis, structures, electrochemistry and magnetic properties of a cyano-bridged {Fe₂Co₂} molecular square

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• 作者：Da-Peng Dong ; Jin-Qiu Xiao ; Peng-Fei Zhuang ; Hui Zheng ; Liang Zhao ; Cheng He ; Tao Liu ; ^{liutao@dlut.edu.cn} ; Chun-Ying Duan ; ^{cyduan@dlut.edu.cn}
• 关键词：Cyanide ; Crystal structure ; Ferromagnetic coupling ; Electrochemistry
• 刊名：Inorganic Chemistry Communications
• 出版年：2012
• 期刊代码：39_13877003
• 类别：ch
• 出版时间：July, 2012
• 卷：21
• 期：Complete
• 页码：84-87
• 文件大小：587 K

摘要

The reaction of tricyanometallate precursor, (Bu₄N)[(Tp*)Fe(CN)₃] (Tp* = hydrotris(3,5-dimethylpyrazol-l-yl)borate) with Co(ClO₄)₂路6H₂O in the presence of the bidentate dpa (dpa = 2,2鈥?dipyridyl amine) ligand affords one novel cyano-bridged heterobimetallic {Fe₂Co₂} molecular square, [Fe^III(Tp*)(CN)₃]₂[Co^II(dpa)₂]₂鈥?ClO₄鈥?H₂O鈥?CH₃OH (1). The molecular structure was determined by single-crystal X-ray diffraction. In compound 1, Fe^III ion is coordinated by three cyanide carbon atoms and three nitrogen atoms of Tp* anions. Whereas, the Co^II ion is surrounded by two cyanide nitrogen atoms and four nitrogen atoms from two bidentate dpa ligands. Cyclic voltammetry (CV) measurements showed that complex 1 exhibited one quasi-reversible waves (0.1 V vs SCE) in the reduction process, and irreversible waves in the oxidation process. Magnetic measurements indicate that complex 1 exhibits a strong intramolecular ferromagnetic interaction between the low-spin Fe^III(S = 1/2) and high-spin Co^II(S = 3/2) ions.