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

包含d-过渡金属离子和镧系离子的异双核络合物

• 批准号: 05640655
• 负责人: SAKAMOTO Masatomi
• 金额: $ 1.34万
• 依托单位: Yamagata University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05640655/
• 关键词: Dinuclear Complex; Lanthanide Complex; Magnetic Property; Fluorescence Property; 希土類錯体

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.

合成并表征了一些新的异核复合物，其中包括D型金属离子和灯笼离子（D-F型异核复合物）。这项工作中使用的隔室配体是N，N'-bis（3-羟基甲基化的）乙二胺，N，N'-BIS（3-羟基甲状腺素化烯）-1,3-丙二胺，N'-bis（3-羧基级别的乙二胺）乙二胺）。基于吸收光谱和圆形二色性，建议氨基醇特异性地结合在D-F杂音中心，通过氮与D-转变金属位点以及通过氧气到灯笼的位点。在这里，应注意的是，NIM（II）-LN（III）复合物配合了氨基al-Cohols，而N，N，N'-Bis（Salicylidene）乙二胺的Ni（II）复合物是平面是方形平面，即使在吡啶类似吡啶的极性溶剂中也没有溶剂。从4.2K到室温的冷冻磁测量表明，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不操作。这些结果表明，应重新研究自旋极化机制，该机制被认为是D型转换金属和灯笼离子之间的磁相互作用的一般机制。欧盟（III）和TB（III）的强荧光在形成异核复合物时显着淬灭。进一步的研究正在进行中，以获取有用的信息，以开发具有各种新功能的复合物。

项目成果

坂本政臣: "Synthesis and Magnctic Property of Heteronuclear Copper(II)-Gadolinium(III)Complexes of Compartmertal Ligands derivel from 2,3-Dihydroxybcnzaldehyde and Diamines" Synthesis and Reactivity in Inorganic and Metal-organic Chemistry. 25(印刷中). (1995)

Masaomi Sakamoto：“源自 2,3-二羟基苯甲醛和二胺的异核铜 (II)-钆 (III) 配合物的合成和磁性”无机和金属有机化学中的合成和反应性 25（出版中）。 (1995)

坂本政臣: "Synthesis and Magentic Property of Heteronuclear Copper(II)-Gadolinium(III) Complexes of Compartmantal ligands derivel from 2,3-dihydroxybenjaldehyde and Diamines" Synthesis and Reactivity in Inorhamic and Metal-orgaric Chemistry. 25(印刷中). (1995)

Masaomi Sakamoto：“源自 2,3-二羟基苯甲醛和二胺的异核铜 (II)-钆 (III) 配合物的合成和磁性”无机化学和金属有机化学中的合成和反应性 25（出版中）。 (1995)

坂本政臣: "Effect of Some d-Transition Mekol Complexes of Salen-Type Ligands and Acetylacetone on Fluorescence of Europium(III)and Terbium(III)" Bulletin of the Chemical Society of Japan. 67. 2707-2711 (1994)

Masaomi Sakamoto：“Salen 型配体和乙酰丙酮的某些 d-Transition Mekol 配合物对铕 (III) 和铽 (III) 荧光的影响”日本化学学会公报 67. 2707-2711 (1994)。

坂本政臣: "Effect of some d-Transition Metal Complexes of Salen-Type Ligands and Acetylacetone of Fluorescencl of Europium(III) and Terbium(III)" Bulletion of the Chemical Society of Japan. 67. 2707-2711 (1994)

Masaomi Sakamoto：“铕 (III) 和铽 (III) 荧光的 Salen 型配体和乙酰丙酮的一些 d-过渡金属配合物的影响” 日本化学会通报 67. 2707-2711 (1994)。

坂本政臣: "Copper(II)-Lanthanide(III)Complexes of Compartmental Ligand,N,N′-Bis(3-hydroxysalicylidene)ethy Lenediamine" Polyhedron. 15(印刷中). (1995)

Masaomi Sakamoto：“房室配体的铜（II）-镧系元素（III）配合物，N,N-双（3-羟基水杨基）乙基二胺”多面体（1995）。