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Two tetranuclear 3d–4f heterometal complexes Mn2Ln2 (Ln = Dy, Gd): synthesis, structure, magnetism, and electrocatalytic reactivity for water oxidation†
New Journal of Chemistry ( IF 3.3 ) Pub Date : 2018-03-09 00:00:00 , DOI: 10.1039/c8nj00149a
Tian-Xiang Lan 1, 2, 3, 4, 5 , Wei-Song Gao 1, 2, 3, 4, 5 , Chang-Neng Chen 6, 7, 8, 9, 10 , Hui-Sheng Wang 11, 12, 13, 14, 15 , Mei Wang 1, 2, 3, 4, 5 , Yu-hua Fan 1, 2, 3, 4, 5
Affiliation  

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 [MnIIMnIIILnIII23-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 (MnII and MnIII) and LnIII 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 (χM′) and in-phase (χM′) 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:

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12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12,这表明这两个复合体可能不是SMM。电化学研究表明,化合物12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。
更新日期:2018-03-09
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