In this present study, two Mn/Ln clusters, [Mn₂Ln₂(O₂CMe)₆(pdmH)₂L](NO₃)·H₂O (Ln = Dy (1), Gd (2)), have been synthesized and experimentally investigated by X-ray crystallography, PXRD, magneto- and electrochemistry. By X-ray analysis, it is shown that the two complexes are isomorphous, both possessing one [Mn^IIMn^IIILn^III₂(μ₃-O)₂]⁶⁺ core with four metal atoms in one plane arranged in a butterfly conformation. This is the first time that mixed-valent manganese (Mn^II and Mn^III) and Ln^III heterometal tetranuclear complexes have been isolated and characterized. Magnetic susceptibility measurements reveal that compounds 1 and 2 both display overall weak ferromagnetic exchanges between the metal ions within the clusters. The temperature dependencies of the out-of-phase (χ_M′) and in-phase (χ_M′) ac susceptibility signals exhibit no significant frequency-dependency for compounds 1 and 2, which suggests that the two complexes may not be SMMs. Electrochemical studies indicate that compounds 1 and 2 can both catalyze water oxidation at a potential of ∼1.70 V with an overpotential of ∼880 mV vs. NHE, which could be due to a cooperative catalytic effect between the manganese and lanthanide ions.

中文翻译：

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两种四核3d–4f杂金属配合物Mn ₂ Ln ₂（Ln = Dy，Gd）：合成，结构，磁性和对水氧化的电催化活性†

在本研究中，两个Mn / Ln团簇[Mn ₂ Ln ₂（O ₂ CMe）₆（pdmH）₂ L]（NO ₃）·H ₂ O（Ln = Dy（1），Gd（2）），已通过X射线晶体学，PXRD，磁化学和电化学方法进行了合成和实验研究。通过X射线分析，其结果表明，两种复合物是同晶型，都具有一个[锰^II的Mn ^III LN ^III ₂（μ ₃ -O）₂ ] ⁶⁺在一个平面上以蝴蝶构型排列的具有四个金属原子的核。这是首次分离并鉴定了混合价锰（Mn ^II和Mn ^III）和Ln ^III杂金属四核配合物。磁化率测量表明，化合物1和2均显示簇内金属离子之间的整体弱铁磁交换。的温度依赖关系的失相（χ_中号'）和相（χ_中号'）的交流磁化率的信号显示出对化合物没有显著频率依赖性1和2，这表明这两个复合体可能不是SMM。电化学研究表明，化合物1和2均可在约1.70 V的电势下催化水氧化，相对于NHE而言，过电势约为880 mV ，这可能是由于锰和镧系离子之间的协同催化作用所致。