Heterodinuclear Complexes Comprising a d-Transition Metal Ion and a Lanthanide Ion

合成了一些由d-过渡金属离子和镧系离子组成的新型杂核配合物（d-f杂核配合物）并进行了表征。本研究使用的区隔配体为N，N'-双（3-羟基水杨酸基）乙二胺、N，N'-双（3-羟基水杨酸基）-1,3-丙二胺和N，N'-双（3-羧基水杨酸基）乙二胺。根据吸收光谱和圆二色性，表明氨基醇在d-f异质金属中心特异结合，通过氮到d-过渡金属位点，通过氧到镧系元素位点。在这里，应该注意的是，Nim (II) -Ln （III）配合物配位于氨基醇，而Ni （II）配合物的N，N'-双（水杨基）乙二胺是方平面的，即使在极性溶剂如吡啶中也不会溶剂化。从4.2K到室温的低温磁测量表明，Cu （II）和Gd （III）离子之间的自旋耦合始终是铁磁性的，而V (IV) O和Gd （III）离子之间的磁相互作用则不发生。这些结果表明，作为d-过渡金属与镧系离子磁相互作用的一般机制，自旋极化机制需要重新研究。Eu （III）和Tb （III）的强荧光在形成异核配合物时被明显猝灭。进一步的研究正在进行中，以期为开发具有各种新功能的复合物提供有用的信息。

Some new heteronuclear complexes comprising a d-transition metal ion and a lanthanide ion (d-f heteronuclear complexes) were synthesized and characterized. The compartmental ligands used in this work are N,N'-bis (3-hydroxysalicylidene) ethylenediamine, N,N'-bis (3-hydroxysalicylidene) -1,3-propanediamine, and N,N'-bis (3-carboxysalicylidene) ethylenediamine. Based on the absorption spectra and the circular dichroism, it was suggested that amino alcohols are specifically bound at the d-f heterometal center, through the nitrogen to the d-transition metal site and through the oxygen to the lanthanide site. Here, it should be noted that the Nim (II) -Ln (III) complexes coordinate the amino al-cohols, whereas the Ni (II) complex of N,N'-bis (salicylidene) ethylenediamine is square planar without solvating even in polar solvent like pyridine. Cryomagnetic measurements from 4.2K to room temperature revealed that the spin coupling between Cu (II) and Gd (III) ions is always ferromagnetic, whereas the magnetic interaction between V (IV) O and Gd (III) ions is not operated. These results indicate that the spin-polarization mechanism, which has been considered as a general mechanism of magnetic interaction between d-transition metal and lanthanide ions, should be reinvestigated. The strong fluorescence of Eu (III) and Tb (III) was markedly quenched on forming the heteronuclear complexes. Further studies are in progress, in order to get an useful information for the development of complexes with various new functions.