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首页> 外文期刊>Chemistry: A European journal >Magnetostructural studies on ferromagnetically coupled copper(II) cubanes of Schiff-base ligands
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Magnetostructural studies on ferromagnetically coupled copper(II) cubanes of Schiff-base ligands

机译：席夫碱配体铁磁耦合铜（II）的磁性结构研究

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Three cubane copper(II) clusters, namely [Cu-4(HL')(4)] (1), [Cu4L2(OH)(2)] (2), and [Cu4L2(OMe)(2)] (3), of two pentadentate Schiff-base ligands N,N'-(2-hydroxypropane-1,3-diyl)bis(acetylacetoneimine) (H3L') and N,N'-(2-hydroxypropane-1,3-diyl)bis(salicylaldimine) (H3L'), are prepared, structurally characterized by Xray crystallography, and their variable-temperature magnetic properties studied. Complex 1 has a metal-to-ligand stoichiometry of 1:1 and it crystallizes in the cubic space group P43n with a structure that consists of a tetranuclear core with metal centers linked by a μ(3)-alkoxo oxygen atom to form a cubic arrangement of the metal and oxygen atoms. Each ligand displays a tridentate binding mode which means that a total of eight pendant binding sites remain per cubane molecule. Complexes [Cu4L2(OH)(2)] (2) and [Cu4L2(OMe)(2)] (3) crystallize in the orthorhombic space group Peen and have a cubane structure that is formed by the self-assembly of two [Cu2L](+) units. The variable-temperature magnetic susceptibility data in the range 300-18 K show ferromagnetic exchange interactions in the complexes. Along with the ferromagnetic exchange pathway, there is also a weak antiferromagnetic exchange between the copper centers. The theoretical fitting of the magnetic data gives the following parameters: J(1)=38.5 and J(2)=-18cm(-1) for 1 with a triplet (S=1) ground state and quintet (S=2) lowest excited state; J(1)=14.7 and J(2)=-18.4 cm(-1) for 2 with a triplet ground state and singlet (S=0) lowest excited state; and J(1)=33.3 and J(2)=-15.6 cm(-1) for 3 with a triplet ground state and quintet lowest excited state, where J(1) and J(2) are two different exchange pathways in the cubane {Cu4O4} core. The crystal structures of 2.6H(2)O and 3.2H(2)O• THF show the presence of channels containing the lattice solvent molecules.
机译：三个古巴铜（II）簇，即[Cu-4（HL'）（4）]（1），[Cu4L2（OH）（2）]（2）和[Cu4L2（OMe）（2）]（3 ）的两个五齿席夫碱配体N，N'-（2-羟基丙烷-1,3-二基）双（乙酰丙酮亚胺）（H3L'）和N，N'-（2-羟基丙烷-1,3-二基）制备了双（水杨基醛亚胺）（H3L'），通过X射线晶体学对其结构进行了表征，并研究了它们的可变温度磁性。配合物1的金属与配体化学计量比为1：1，并且在立方空间群P43n中结晶，该结构由四核核组成，四核核的金属中心通过μ（3）-烷氧基氧原子连接而形成立方金属和氧原子的排列。每个配体均显示三齿结合模式，这意味着每个古巴分子总共保留八个侧基结合位点。复合物[Cu4L2（OH）（2）]（2）和[Cu4L2（OMe）（2）]（3）在正交空间群Peen中结晶，并具有由两个[Cu2L ]（+）个单位。 300-18 K范围内的可变温度磁化率数据显示了配合物中的铁磁交换相互作用。除铁磁交换路径外，铜中心之间的反铁磁交换也较弱。磁数据的理论拟合给出以下参数：对于具有三重态（S = 1）基态和最低五重奏（S = 2）的1，J（1）= 38.5和J（2）=-18cm（-1）兴奋状态对于具有三重态基态和单重态（S = 0）最低激发态的2，J（1）= 14.7和J（2）=-18.4 cm（-1）;和J（1）= 33.3和J（2）=-15.6 cm（-1）的3具有三重态基态和五重态最低激发态，其中J（1）和J（2）是两种不同的交换路径古巴{Cu4O4}核心。 2.6H（2）O和3.2H（2）O＆BULL的晶体结构; THF显示存在包含晶格溶剂分子的通道。

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