Metal Complexes in Extended Systems : Design and Magnetism

扩展系统中的金属配合物:设计和磁性

• 批准号: 09044093
• 负责人: OKAWA Hisashi
• 金额: $ 6.46万
• 依托单位: KYUSHU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09044093/
• 关键词: Ferrimagnet; Metamegnet; Bimetallic compound; Diazine ligands; Magnetic ordering; Network compound; Bridging ligand; Spontaneous magnetization; ヘテロ多核鎖体; 伸展型錯体; メタ磁性体; フェロ磁性体; 磁気交換; 双性配位子; 自発磁化; 架橋配位子

1. Bimetallic Magnetic Materials Extended by M-Cn-M' Linkages1) 2-Dimencional bimetallic compounds [Ni(diamine)ィイD22ィエD2]ィイD22ィエD2 [Fe(Cn)ィイD26ィエD2] X have been prepared which have a square-sheet structure extended through FeィイD1IIIィエD1-CN-NiィイD1IIィエD1 linkages with Fe ions at the coiners and Ni ions at the edges. A ferromagnetic interaction operates within the sheet. The overall magnetic property is governed by the intersheet separation : a small intersheet separation (<10 Å) gives metamagnets owing to intersheet antiferromagnetic interaction whereas a large intersheet separation (>10 Å) provides ferromagnets. The intersheet separation can be controlled by the choice of counter ion and the hydration water.2) 3-Dimencional bimetallic assemblies [Ni(L)ィイD22ィエD2]ィイD23ィエD2[FeィイD1IIィエD1(CN)ィイD26ィエD2]XィイD22ィエD2 (L=en, tn ; X=PFィイD26ィエD2ィイD1-ィエD1, CIOィイD24ィエD2ィイD1-ィエD1) have been prepared and structurally characterized. They have an isotropic cubic network with Fe ions at the corners and Ni … More ions on the edges.Magnetic studies indicates a ferromagnetic interaction between the nearest Ni ions thorough the diamagnetic Fe ion.3) A bimetallic assembly [(Mn)en]ィイD23ィエD2[Cr(CN)ィイD26ィエD2]ィイD22ィエD2 ・4HィイD22ィエD2O was obtained which has a defective cubane structure with three Cr atoms and four atoms at the seven corners and eight Cr-CN-Mn edges. Based on magnetization (FCM, ZFCM, RM) and hysteresis studies, it was fount to be a ferrimagnet showing magnetic ordering below 69 K. To the best of our knowledge, the Tc is the highest among the structurally characterized molecular-based magnets.2. Magnetism of Dinuclear CuィイD1IIィエD1 Complexes Bridged by Diazine LigandsDinuclear CuィイD1IIィエD1 complexes of three polydantate diazine ligands, based on potentially bridge N-N single bond fragments, were studied. The magnetic interaction between the two CuィイD1IIィエD1 ions is markedly dependent upon the torsion angle between the two Cu chromophores with respect to the N-N bond. In general, a large distortion angle results in no spin-coupling and a small distortion causes a strong antiferromagnetic interaction.3. New strategy for Magnetic MaterialsA new bridging ligand having an oxamidate and a glyoxymate groups (HィイD24ィエD2L) was prepared. Its CuィイD1IIィエD1 complex [Cu(HL)]ィイD1-ィエD1 was synthesized in situ and reacted with a second MィイD1IIィエD1 ion to provide trinuclear CuィイD1IIィエD1-MィイD1IIィエD1-CuィイD1IIィエD1 complexes [M{Cu(HL)}ィイD22ィエD2(dmf)ィイD22ィエD2]/2dmf (M=Mn, Co, Ni, Zn) were obtained. The [Cu(HL)]ィイD1-ィエD1 entity form a planar {CuNィイD24ィエD2} chromophore with the hydrogen-bonded N-O-H-N-O chelate. Two {Cu(HL)ィイD22ィエD2ィイD1-ィエD1 molecules coordinate to the MィイD1IIィエD1 ion providing an octahedral geometry together with two dmf molecules. [Mn{Cu(Hl)}]ィイD22ィエD2(dmf)ィイD22ィエD2・2(dmf)ィイD22ィエD2}2dmf was reacted with MnィイD1IIィエD1 ion in the presence of KィイD1+ィエD1 and 18-crown-OィイD26ィエD2 to provide an ordered system exhibiting a spontaneous magnetization at 5.5 K. This work illustrates a stepwise synthesis of bimetallic magnets using a designed bridging ligand. Less

1. Bimetallic Magnetic Materials Extended by M-Cn-M' Linkages1) 2-Dimencional bimetallic compounds [Ni(diamine)IIID22IID2]IID22IID2 [Fe(Cn)IID26IID2] X have been prepared which have a square-sheet structure extended through FeiD1IIIID1-CN-NiID1IIIID1 linkages with Fe ions at the coiners and Ni离子边缘。铁磁相互作用在纸板内部运行。整体磁性特性受互面部分离的控制：由于互式抗磁性抗铁磁相互作用，一个小的互面间隔（<10Å）给出了元磁体，而大型互插分离（>10Å）提供了效能电磁体。 The intersheet separation can be controlled by the choice of counter ion and the hydration water.2) 3-Dimencional bimetallic assemblies [Ni(L)D22E D2]D23E D2[Fe D1IIE D1(CN)D26E D2]XIE D22E D2 (L=en, tn ; X=PFID D26E D2II D1-E D1, CIOI D24E D2II D1-E D1）已经制备并在结构上表征。他们具有一个各向同性的立方网络，在角落和ni上有fe离子……更多的离子在边缘上。磁性研究表明最近的ni离子3）双金属组装[（mn）d23e d2 d2 d2 [cr（cn）d26e d2 d2 d2 d2] d22e d22e d2 cubs a bimetalic组装[（mn）en]在七个角和八个CR-CN-MN边缘的三个Cr原子和四个原子的结构。基于磁化强度（FCM，ZFCM，RM）和磁滞研究，是一个富含磁性秩序的磁性储备，这是一个低于69 K.的磁性序列。据我们所知，TC是结构上具有分子基于分子的磁体中最高的。2。研究了基于潜在的桥接N-N单键片段的三种多丹酸酯配体的双氮氨酸配体cuィイd1ii d1ii d1ii d1ii d1复合物桥接的D1II d1复合物的磁性。两个Cuィイd1ii d1离子之间的磁相互作用明显取决于两个Cu发色团之间相对于N-N键的扭转角。通常，较大的失真角会导致无自旋偶联，而较小的失真会导致强烈的抗铁磁相互作用。3。磁性材料的新策略制备了具有含氧剂和乙醛酸酯基（HII D24 E D2L）的新桥接配体。它的CuI D1II E D1复合物[Cu（Hl）] II D1-E D1在原位合成，并与一秒钟的我的D1III D1 ION反应，以提供三核Cu（HL）} II D22（DMF）II D22（DMF）II D22] II D22]/2DMF（M = M = MN，CO，ni，ni，Zn）。 [Cu（Hl）] II D1-II D1实体形成了平面{Cuni D24 D2}发色团带有氢键的N-O-H-N-O Cherry。两个{Cu（HL）II D22 D2-II D1-II D1分子与MII D1III D1离子坐标，提供八面体几何形状以及两个DMF分子。 [Mn{Cu(Hl)}]D22(dmf)D22 ion was reacted with MnII D1 III D1 ion in the presence of K1+ ie D1 and 18-crown-oy D26 to provide an ordered system exhibiting a sponsorous magnetization at 5.5 K. This work illustrates a stepwise synthesis of bimetallic magnets using a designed bridging ligand.较少的

项目成果

M. Sasaki: "A novel Discrete d-f Heterobinuclear Complex Designed from Tetrahedrally distorted [Cu(salabza)] and [Gd(hfac)_< 3>]"Chem. Lett.. 911-912 (1998)

M. Sasaki：“一种由四面体扭曲 [Cu(salabza)] 和 [Gd(hfac)_< 3>] 设计的新型离散 d-f 异双核配合物”Chem.

M. Ohba, N. Fukita, and H. Okawa: "Magnetic Characteristics of Bimetallic Assembles, [Ni(en)ィイD22ィエD2]ィイD23ィエD2[M(CN)ィイD26ィエD2]ィイD22ィエD2・2HィイD22ィエD2O (M=Fe, Cr or Co), with a 1-D1Ropeladder Chain Structure"J. Chem. Soc., Dalton Trans.. (No. 10). 1733-1737

M. Ohba、N. Fukita 和 H. Okawa：“具有 1-D1Ropeladder 链结构的双金属组件 D22D2·2HD22D2O（M=Fe、Cr 或 Co）的磁性”J. ..（第10号）。1733年-1737年。

K. Takahashi, J. Shimada, M. Itoh, Y. Fuchida, and H. Okawa: "Synthesis and Characterization of Triple-decker Sandwich Dinuclear La(III) and Lu(III) Complexes of 2, 3, 9, 10, 16, 17, 23, 24-Octabutoxy-phthalocyanine"Chem. Lett.. (No. 2). 173-174 (1998)

K. Takahashi、J. Shimada、M. Itoh、Y. Fuchida 和 H. Okawa：“2、3、9、10 的三层夹心双核 La(III) 和 Lu(III) 配合物的合成和表征，

Nobuo Fukita: "Bimetallic Assemblies, [Ni (L)_2]_3 [Fe (CN)_6] X_2 (L=en,tn ; X=PF_6^-,ClO_4^-),with a 3-D Network Extended through Fe^<II>-CN-Ni^<II> Linkages" Inorganic Chemistry. (現在発行予定である).

Nobuo Fukita：“双金属组件，[Ni (L)_2]_3 [Fe (CN)_6] X_2 (L=en,tn ; X=PF_6^-,ClO_4^-)，具有通过 Fe 扩展的 3-D 网络^<II>-CN-Ni^<II> Linkages”无机化学。（目前计划出版）。

大川尚士: "金属イオンを集積させて磁性体を創る"化学と工業. 51・9. 1420-1423 (1999)

Naoshi Okawa：“通过积累金属离子来制造磁性材料”化学与工业 1420-1423（1999）。