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.

在本研究项目中，我们致力于建立合理的3D-4F混合金属络合物的合成方法，并对其物理性质进行了系统的研究。2000-2002年的主要结果如下：1.M^&lt；II&gt；-Ln^&lt；III&gt；-M^&lt；II&gt；型三核配合物[M_2LN(L)_2(NO_3)_3](M^&lt；II&gt；=Mn，Fe，Co，Ni，Cu，Zn；Ln^&lt；III&gt；=La，Ce，...1，1‘-(2，6-吡啶基)-双(L，3-丁二酮)(H_2L)、M(NO_3)_2NH_2O和Ln(NO_3)_3NH_2O通过不同的离子半径“一锅”反应得到。测定了大部分配合物的晶体结构。提供一个中心2，6-二酰基吡啶中心和两个末端1，3-二酮基中心的两个L离子在所有配合物中都含有两个M^&lt；II&gt；离子和Ln^&lt；III&gt；离子，并形成一个线性的M-Ln-M三核核。三核核的平面度随Ln^&lt；III&gt；离子的变化而变化。两个吡啶环之间的二面角随着中心离子半径的减小而增大。反铁磁相互作用在M^&lt；II&gt；和Ln^&lt；III&gt；(f^1-f^6)之间起作用。另一方面，M^&lt；II&Gt；和Ln^&lt；III&Gt；(Gd，Dy，Tb)之间的磁相互作用明显是铁磁性的。而另一种稀土离子由于主要的自旋-轨道耦合作用而表现出反铁磁性行为。由三核配合物[M_2LN(L)_2(NO_3)_3]和[Cr(CN)_6]^&lt；3-&gt；合成了新型三金属配合物[M_2Gd(L)_2][Cr(CN)_6]·nH_2O。M=Cu为一维链状结构，M=Ni为二维片状结构，M=Co为三维网状结构。在M=Ni和Co的情况下，实现了磁有序。此外，根据中心Ln^&lt；III和Gt；离子的不同，Coln-Cr组件显示出铁、铁和亚磁有序。

项目成果

Naoki Usuki et al.: "A Bimetallic Magnetic System Exhibiting Reversible Ferromagnetism/Metamagnetism Modulation"Bulletin of the Chemical Society of Japan. 75・8. 1693-1698 (2002)

Naoki Usuki 等人：“展示可逆铁磁性/超磁性调制的双金属磁系统”日本化学学会公报 75・8 (2002)。

大場 正昭: "New 3-D Bimetallic Magnetic Compounds, [Ni(dipn)]_3[M(CN)_6]_2.7H_2O (M^<III> = Fe, Co dipn = N, N-di(3-aminopropyl)amine)"Molecular Crystals and Liquid Crystals. 379. 241-246 (2002)

Masaaki Ohba：“新型 3-D 双金属磁性化合物，[Ni(dipn)]_3[M(CN)_6]_2.7H_2O (M^<III> = Fe, Co dien = N, N-二(3-氨基丙基) )胺)”分子晶体和液晶。379. 241-246 (2002)

Masaaki Ohba et al.: "Novel Trinuclear Cu(II)_2Gd(III) Compound Derived from Macrocyclic dinuclear Cu(II)_2 Complex"Polyhedron. (発表予定). (2003)

Masaaki Ohba 等人：“源自大环双核 Cu(II)_2 复合物的新型三核 Cu(II)_2Gd(III) 化合物”多面体（即将出版）。

志賀 拓也: "Structure and magnetism of a trinuclear Cu^<II>-Gd^<III>-Cu^<II> complex derived from one-pot reaction with 2,6-di(acetoacetyl)pyridine"Inorganic Chemistry Communications. 6. 15-18 (2003)

Takuy​​a Shiga：“由 2,6-二（乙酰乙酰基）吡啶一锅反应衍生的三核 Cu^<II>-Gd^<III>-Cu^<II> 络合物的结构和磁性”无机化学通讯 6。 .15-18 (2003)

大場 正昭: "Magneto-optical Properties of Two-dimensional Cyanide-bridged M^<III>-Ni^<II> Bimetallic Assemblies (M = Fe, Co)"Chemistry Letters. 10. 1046-1047 (2002)

Masaaki Ohba：“二维氰化物桥 M^<III>-Ni^<II> 双金属组件 (M = Fe, Co) 的磁光性质”《化学快报》10. 1046-1047 (2002)