Access to Heteroleptic Fluorido‐Cyanido Complexes with a Large Magnetic Anisotropy by Fluoride Abstraction
Access to Heteroleptic Fluorido‐Cyanido Complexes with a Large Magnetic Anisotropy by Fluoride Abstraction
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通过氟化物提取获得具有大磁各向异性的杂配氟氰基配合物
DOI：
10.1002/anie.201914934
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发表时间：
2020
期刊：
影响因子：
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通讯作者：
Durand, Etienne
中科院分区：
文献类型：
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作者：
Liu, Jun‐Liang;Pedersen, Kasper S.;Greer, Samuel M.;Oyarzabal, Itziar;Mondal, Abhishake;Hill, Stephen;Wilhelm, Fabrice;Rogalev, Andrei;Tressaud, Alain;Durand, Etienne
硅介导的氟化物提取被证明是产生第一个氟氰基过渡金属络合物的手段。这种新的合成方法的例子是杂配配合物trans-[MIVF 4（CN）2]2−（M=Re，Os）的合成和表征，该配合物是从它们的同配型[MIVF 6]2−母体获得的。正如高场电子顺磁共振谱和磁化强度测量所显示的那样，氰化物配体部分取代氟化物导致反式-[ReF 4（CN）2]2−的磁各向异性比[ReF 6]2−显著增加，反映了严重偏离理想的八面体（Ohpoint群）配体场。这种方法为实现新的混配过渡金属配合物铺平了道路，这些配合物可用作高性能分子基磁性材料设计的高度各向异性构建块。
Silicon‐mediated fluoride abstraction is demonstrated as a means of generating the first fluorido‐cyanido transition metal complexes. This new synthetic approach is exemplified by the synthesis and characterization of the heteroleptic complexes,trans‐[MIVF4(CN)2]2−(M=Re, Os), obtained from their homoleptic [MIVF6]2−parents. As shown by combined high‐field electron paramagnetic resonance spectroscopy and magnetization measurements, the partial substitution of fluoride by cyanide ligands leads to a marked increase in the magnetic anisotropy oftrans‐[ReF4(CN)2]2−as compared to [ReF6]2−, reflecting the severe departure from an ideal octahedral (Ohpoint group) ligand field. This methodology paves the way toward the realization of new heteroleptic transition metal complexes that may be used as highly anisotropic building‐blocks for the design of high‐performance molecule‐based magnetic materials.