Rational and systematic syntheses and physical properties of 3d-4f mixed metal complexes

3d-4f混合金属配合物的合理系统合成及物理性质

• 批准号: 13640561
• 负责人: OHBA Masaaki
• 金额: $ 2.37万
• 依托单位: KYUSHU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13640561/
• 关键词: Lanthanide; 3d-4f mixed metal complexes; Spin-orbit coupling; Trimetallic assemblies; Molecular-based Magnets; magnetic ordering; 強磁性的相互作用

In this research program, we focused on establishment of rational synthesis method for 3d-4f mixed metal complexes and systematic investigation of their physical properties. Principal results during 2000-2002 are as follows.1. M^<II>-Ln^<III>-M^<II> type trinuclear complexes, [M_2Ln(L)_2(NO_3)_3] (M^<II> = Mn, Fe, Co, Ni, Cu, Zn ; Ln^<III> = La, Ce, ... Yb, Lu), were successfully obtained from a 'one-pot' reaction of a ligand, 1, 1'-(2, 6-pyridylene)-bis(l, 3-butanedione) (H_2L), M(NO_3)_2nH_2O and Ln(NO_3)_3nH_2O with using of difference of ion radius.2. Crystal structures of most of complexes were determined. Two L^<2-> providing one central 2, 6-diacylpyridine site and two terminal 1, 3-diketonate sites hold two M^<II> ions and Ln^<III> ion and form a linear M-Ln-M trinuclear core in all complexes. The planarity of the trinuclear core changes with the Ln^<III> ion. The dihedral angle between two pyridine rings increases with decreasing ion radius of central Ln^<III>.3. Antiferromagnetic interaction operates between M^<II> and Ln^<III> (f^1 - f^6). On the other hand, magnetic interaction between M^<II> and Ln^<III> (Gd, Dy, Tb) are clearly ferromagnetic. However, the other lanthanide ion shows antiferromagnetic behavior because of dominant spin-orbit coupling.4. Novel trimetallic assemblies, [M_2Gd(L)_2][Cr(CN)_6]・nH_2O, were prepared by the reaction of the trinuclear complexes, [M_2Ln(L)_2(NO_3)_3], and [Cr(CN)_6]^<3->. The assembled structure was 1-D chain for M = Cu, 2-D sheet for M = Ni, and 3-D network for M =Co, respectively. In the case of M = Ni and Co, magnetic ordering was achieved. Furthermore, CoLn-Cr assemblies show ferro-, ferri- and meta-magnetic ordering depending on the central Ln^<III> ions.

本课题主要致力于建立3d-4f混合金属配合物的合理合成方法并对其物性进行系统研究，主要研究成果如下： 1． >-M^<II>型三核配合物，[M_2Ln(L)_2(NO_3)_3] (M^<II> = Mn、Fe、Co、Ni、Cu、Zn； Ln^<III> = La, Ce, ... Yb, Lu) 是通过配体 1, 1'-(2, 6-亚吡啶基)-双(l,利用离子半径的差异分析了3-丁二酮)(H_2L)、M(NO_3)_2nH_2O和Ln(NO_3)_3nH_2O。2．确定了两个L^2-提供一个中心2，6-二酰基吡啶位点和两个末端1，3-二酮位点，其持有两个M^<II>离子和Ln^<III>离子并形成线性M-Ln。所有配合物中的-M 三核核心的平面度随Ln^<III>离子的变化而变化。两个吡啶环之间的二面角随着离子半径的减小而增大。中心 Ln^<III>.3。M^<II> 和 Ln^<III> 之间存在反铁磁相互作用 (f^1 - f^6)，而 M^<II> 和 Ln^ 之间存在磁相互作用。 <III>（Gd、Dy、Tb）明显是铁磁性的，然而，由于占主导地位的自旋轨道耦合，其他镧系元素离子表现出反铁磁性。4．通过三核配合物[M_2Ln(L)_2(NO_3)_3]和[Cr(CN)_6]^的反应制备了组件[M_2Gd(L)_2][Cr(CN)_6]・nH_2O <3->. 组装的结构分别为M = Cu 的一维链、M = Ni 的二维片材和M = Co 的3-D 网络。在 M = Ni 和 Co 的情况下，实现了磁排序。此外，CoLn-Cr 组件显示出取决于中心 Ln^<III> 离子的铁磁、亚铁磁和变磁排序。