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首页> 外文期刊>Chemistry: A European journal >Structures and Magnetic Properties of Tetranuclear Nickel(n) Complexes with Unusual mu_3-l,l,3 Azido Bridges
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Structures and Magnetic Properties of Tetranuclear Nickel(n) Complexes with Unusual mu_3-l,l,3 Azido Bridges

机译：具有异常mu_3-1，l，3叠氮桥的四核镍（n）配合物的结构和磁性

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摘要

Pyrazolate-based dinucleat-ing ligands with thioether-containing chelate arms have been used for the synthesis of a family of novel tetranuclear nickel(II) complexes [L_2Ni_4(N_3)_3(O_2CR)](ClO_4)_2 that incorporate three azido bridges and one car-boxylate (R = Me,Ph).Molecular structures have been elucidated by X-ray crystallography in four cases,revealing Ni_4 cores with a unique topology in which two of the azido ligands adopt an unusual mu_3-1,1,3 bridging mode.The compounds were further characterized by mass spectrometry,IR spectroscopy,and variable-temperature magnetic susceptibility measurements.Magnetic data analyses indicate a combination of significant intramolecular ferromagnetic and antiferromagnetic exchange interactions that give rise to an overall S_T = 0 ground state.The sign and the magnitude of the individual couplings have been rationalized in the framework of the common magne-tostructural correlations for end-to-end and end-on azido linkages,suggesting that these correlations also remain valid for the respective fragments of multiply bridging mu_3-1,1,3 azido ligands.
机译：具有含硫醚螯合臂的基于吡唑酸酯的双核配体已用于合成新型三核镍（II）配合物[L_2Ni_4（N_3）_3（O_2CR）]（ClO_4）_2家族，该配合物包含三个叠氮桥和X射线晶体学已经阐明了四种结构的分子结构，揭示了具有独特拓扑结构的Ni_4核，其中两个叠氮配体采用了不寻常的mu_3-1,1,3化合物通过质谱，红外光谱和可变温度磁化率测量进一步表征。磁性数据分析表明，分子内强铁磁和反铁磁交换相互作用结合在一起，导致整体S_T = 0基态。在端对端和端对叠氮基连接的常见镁-结构相关性框架内，合理化了各个耦合的符号和强度。对于多重桥接mu_3-1,1,3叠氮基配体的各个片段，相关关系也仍然有效。

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