Structures, Magnetic Properties, and Reactivity Studies of Salts Containing the Dinuclear Anion [M2Cl6]2- (M = Mn, Fe, Co)
Structures, Magnetic Properties, and Reactivity Studies of Salts Containing the Dinuclear Anion [M2Cl6]2- (M = Mn, Fe, Co)
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含有双核阴离子 [M2Cl6]2- (M = Mn、Fe、Co) 的盐的结构、磁性和反应性研究
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发表时间：
1999
期刊：
影响因子：
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通讯作者：
K. Dunbar
中科院分区：
文献类型：
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作者：
Jui;Hanhua Zhao;X. Ouyang;R. Clérac;Jennifer A. Smith;J. Clemente;C. Gómez‐García;A. E. Coronado;K. Dunbar
以MCl2与1等量氯离子反应，制备了M = Mn、Fe、Co的边沿共享双面体阴离子[M2Cl6]2-盐。用[PPh4]+(1)、[Et4N]+(2)、[ppn]+(3)、[AsPh4]+(4)和[H-TMPP]+ (5) ([H-TMPP]+ =三（2,4,6-三甲氧基苯基）磷分离阴离子[Fe2Cl6]2-；[ppn]+ =二（三苯基磷）氯化亚胺。Mn和Co化合物分离为[ppn]+盐，[ppn]2[Co2Cl6](6)和[ppn]2[Mn2Cl6](7)。化合物通过单晶x射线分析和变温度和场相关磁测量进行了表征。这些磁数据是从自旋哈密顿量中分析出来的，该哈密顿量包含一个各向同性交换项，补充了一个零场分裂项，以解释相互作用自旋的单离子各向异性。通过这种方法，[Fe2Cl6]2-盐（1−5）表现出由四合体自旋S = 2的单离子各向异性主导的磁性行为。
Salts of the edge-sharing bitetrahedral anion [M2Cl6]2- with M = Mn, Fe, and Co were prepared in high yields by reaction of MCl2 with 1 equiv of chloride ion. The anion [Fe2Cl6]2- was isolated with five different cations, namely, [PPh4]+ (1), [Et4N]+ (2), [ppn]+ (3), [AsPh4]+ (4), and [H-TMPP]+ (5) ([H-TMPP]+ = tris(2,4,6-trimethoxyphenyl)phosphonium; [ppn]+ = bis(triphenylphosphonium)iminium chloride). The Mn and Co compounds were isolated as [ppn]+ salts, [ppn]2[Co2Cl6] (6) and [ppn]2[Mn2Cl6] (7). The compounds were characterized by single-crystal X-ray analysis and subjected to variable-temperature and field-dependent magnetic measurements. These magnetic data were analyzed from a spin Hamiltonian that contains an isotropic exchange term supplemented by a zero-field-splitting term to account for the single-ion anisotropy of the interacting spins. By using this approach, the [Fe2Cl6]2- salts (1−5) were shown to exhibit magnetic behavior dominated by single-ion anisotropy of the spin S = 2 of the tetrahe...