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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >Synthesis, structures and magnetic properties of two hexanuclear complexes
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Synthesis, structures and magnetic properties of two hexanuclear complexes

机译：两种六核配合物的合成，结构和磁性

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摘要

The reaction of salicylaldoxime (H(2)salox) With Mn(ClO4)(2) center dot 6H(2)O, NaN(CN)(2) and NEt3 in MeOH affords a Mn-6(III) hexanuclear complex of [Mn6O2(salox)(6)(MeOH)(6)(NCNCONH2)(2)] (1), while reaction of H(2)salox With MnCl2 center dot 4H(2)O and NEt4OH in EtOH affords a Mn-6(III) hexanuclear complex of [Mn6O2(salox)(6)(EtOH)(4)(H2O)(2)Cl-2] (2). Both complexes 1 and 2 contain a [Mn-6(III)(mu(3)-O)(2)](14+) core, which is a known structural type in the family of Mn-6 complexes. Variable temperature magnetic susceptibilities and magnetization measurement of complexes 1 and 2 have been carried out. Exchange interactions of metal centers for complexes 1 and 2 are fitted by a full diagonalization matrix method. The fitting results indicate that both complexes 1 and 2 have the ground-state spin value of S = 4, and the ground state of complex 1 has the much closer energy to low-lying spin states than that of complex 2. Magnetization measurements at 2.0-4.0 K and 10-70 kG confirm that the ground state is S = 4, with significant magnetoanisotropy as gauged by the D value of -0.82 cm(-1) and -1.18 cm(-1), for 1 and 2, respectively. The frequency dependence of the out-of-phase component in alternating current magnetic susceptibilities for both complexes 1 and 2 indicates the slow magnetic relaxation of superparamagnetic behaviour with a U-eff of 27.0(1) K and tau(0) = 3.8(2) x 10(-9) s for complex 1, and U-eff of 25.1(6) K and tau(0) = 4.6(1) x 10(-8) s for complex 2.
机译：水杨醛肟（H（2）salox）与Mn（ClO4）（2）中心点6H（2）O，NaN（CN）（2）和NEt3在MeOH中的反应得到[[Mn-6（III））六核配合物Mn6O2（salox）（6）（MeOH）（6）（NCNCONH2）（2）]（1），而H（2）salox与MnCl2中心点4H（2）O和NEt4OH在EtOH中的反应得到Mn-6 （III）[Mn6O2（salox）（6）（EtOH）（4）（H2O）（2）Cl-2]的六核络合物（2）。配合物1和2都包含[Mn-6（III）（mu（3）-O）（2）]（14+）核，这是Mn-6配合物家族中已知的结构类型。已经对配合物1和2进行了可变温度磁化率和磁化测量。配合物1和2的金属中心的交换相互作用通过完全对角化矩阵方法拟合。拟合结果表明，配合物1和2的基态自旋值为S = 4，并且配合物1的基态能量比配合物2的低自旋态更接近低能旋转状态。在2.0时的磁化强度测量-4.0 K和10-70 kG确认1和2的基态为S = 4，具有显着的磁各向异性，分别由-0.82 cm（-1）和-1.18 cm（-1）的D值测量。配合物1和2的交流磁化率中异相分量的频率依赖性表明超顺磁行为的慢磁弛豫，U-eff为27.0（1）K，tau（0）= 3.8（2） ）x 10（-9）s（对于复数1），U-eff为25.1（6）K，tau（0）= 4.6（1）x 10（-8）s（对于复数2）。

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