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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Structures and magnetic properties of Mn~(III)_4Ln ~(III)_4 aggregates with a 'square-in-square' topology
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Structures and magnetic properties of Mn~(III)_4Ln ~(III)_4 aggregates with a 'square-in-square' topology

机译:Mn〜(III)_4Ln〜(III)_4聚集体的结构和磁性

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The structures and magnetic properties of a family of new octanuclear heterometallic 3d-4f complexes [Mn~(III)_4Ln ~(III)_4(μ_3-OH)_4(μ_2, η~1-X)_4(O_2CBu~t) _8(t-bdea)_4]·solv, where X = N_3~-, Ln = Y (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6); X = OCN ~-, Ln = Dy (7); X = NO_3~-, Ln = Gd (8), Tb (9), Dy (10), Ho (11), Er (12); solv = MeCN or toluene, are reported. The metal topology in the aggregates can be described as consisting of a "Ln _4-square inscribed in a Mn_4-square". Complexes 1-7 are prepared by the reactions of t-butyldiethanolamine (t-bdeaH_2) with a preformed hexanuclear manganese pivalate complex [Mn_6], the respective lanthanide salt and either NaN_3 or NaNCO, while 8-12 are obtained from the direct reaction of Mn(OAc)_2, Ln(NO _3)_3·xH_2O and t-butyldiethanolamine. The magnetic properties of all the complexes were investigated using variable temperature magnetic susceptibility and magnetisation measurements. Similar magnetic behaviour was observed for compounds containing the same lanthanide, indicating that changing the bridging ligand X does not have a significant effect on the magnetic behaviour. The Tb~(III) and Dy~(III) compounds 4, 5, 7, 9 and 10 all show frequency-dependent ac susceptibilities indicative of a slow relaxation of magnetisation and are therefore considered as Single-Molecule Magnets.
机译:新型八核杂多金属3d-4f配合物[Mn〜(III)_4Ln〜(III)_4(μ_3-OH)_4(μ_2,η〜1-X)_4(O_2CBu〜t)_8的结构和磁性(t-bdea)_4]·solv,其中X = N_3〜-,Ln = Y(1),Eu(2),Gd(3),Tb(4),Dy(5),Ho(6); X = OCN〜-,Ln = Dy(7); X = NO_3〜-,Ln = Gd(8),Tb(9),Dy(10),Ho(11),Er(12);报告了solv = MeCN或甲苯。聚集体中的金属拓扑可以描述为由“刻在Mn_4平方中的Ln -4-平方”组成。配合物1-7是通过叔丁基二乙醇胺(t-bdeaH_2)与预先形成的六核新戊酸锰配合物[Mn_6],相应的镧系元素盐和NaN_3或NaNCO反应制备的,而8-12是由Mn(OAc)_2,Ln(NO _3)_3·xH_2O和叔丁基二乙醇胺。使用可变温度磁化率和磁化强度测量研究了所有配合物的磁性。对于包含相同镧系元素的化合物,观察到了相似的磁行为,这表明改变桥联配体X对磁行为没有显着影响。 Tb_(III)和Dy_(III)化合物4、5、7、9和10均显示出随频率变化的磁化率,表明磁化作用缓慢松弛,因此被认为是单分子磁体。

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