权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

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.

本研究主要致力于3d-4f混配金属配合物的合理合成方法的建立和物理性质的系统研究。2000-2002年期间的主要成果如下。M^<II>-Ln^<III>-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，...利用离子半径的差异，通过配体1，1 '-（2，6-吡啶基）-双（1，3-丁二酮）（H_2L）、M（NO_3）_2nH_2O和Ln（NO_3）_3nH_2O的“一锅法”反应，成功地合成了Yb，Lu）.测定了大部分配合物的晶体结构。在所有配合物中，两个L2<2->提供一个中心的2，6-二酰基吡啶位点和两个末端的1，3-二酮基位点，它们容纳两个M2<II>离子和Ln 2<III>离子，并形成线性的M-Ln-M三核核心。三核芯的平面性随着Ln^+离子的变化而变化<III>。两个吡啶环之间的二面角随着中心Ln^3的离子半径的减小而增大<III>。反铁磁相互作用在M^<II>和Ln^<III>（f^1 - f^6）之间起作用。另一方面，M^<II>和Ln^<III>（Gd，Dy，Tb）之间的磁相互作用明显是铁磁的。而另一种镧系离子由于自旋轨道耦合占主导地位，表现出反铁磁行为.通过三核配合物[M_2Ln（L）_2（NO_3）_3]和[Cr（CN）_6]~（2-）的反应，合成了新型的三金属配合物[M_2Gd（L）_2][Cr（CN）_6]·nH_2O<3->。组装结构为一维链状（M = Cu）、二维片状（M = Ni）和三维网状（M =Co）。在M = Ni和Co的情况下，实现了磁有序。此外，CoLn-Cr组装体显示铁磁性、铁磁性和亚磁性有序，这取决于中心Ln 2<III>离子。