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

基本信息

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

项目摘要

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.

在该研究计划中，我们专注于建立用于3D-4F混合金属复合物的合理合成方法和对其物理特性的系统投资。 2000 - 2002年期间的主要结果如下1。 m^<ii> -ln^<iii> -m^<ii>型三核复合物，[m_2ln（l）_2（no_3）_3]（m^<ii> = Mn，fe，fe，fe，co，ni，ni，cu，cu，zn; ln^<iii> = la，ce，... ce，... yb，lu） 6-pyridylene）-bis（l，3-丁烷二酮）（H_2L），M（no_3）_2NH_2O和LN（NO_3）_3NH_2O，使用离子半径差2。确定了大多数配合物的晶体结构。两个L^<2->提供一个中央2，6-二酰吡啶位点和两个末端1，3-二甲酸位点，在所有配合物中都有两个M^<ii>离子和Ln^<iii>离子，并形成线性M-LN-M三核核心。三核核心的平面性随ln^<iii>离子而变化。两个吡啶环之间的二面角随着中央Ln^<iii> .3的离子半径的减小而增加。抗铁磁相互作用在M^<ii>和Ln^<iii>之间起作用（f^1 -f^6）。另一方面，M^<ii>和Ln^<iii>（GD，DY，TB）之间的磁相互作用显然是铁磁。然而，另一个灯笼离子显示出抗铁磁性行为，这是由于显性旋转轨道耦合的4。通过三核配合物的反应制备了新型的三金属组件，[m_2gd（l）_2] [Cr（cn）_6] nh_2o，[m_2ln（l）_2（no_3）_3]和[CR（CN（CN）_6] _6] _6] _6] _6 _6]^<3-->。组装结构分别为M = Cu，M = Ni的2-D板和M = CO的3-D网络。在M = Ni和CO的情况下，实现了磁顺序。此外，COLN-CR组件根据中央Ln^<iii>离子显示出铁，铁和元磁性排序。