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)2-二金属双金属化合物[Ni(Diamine)ィイD22ィエD2]ィイD22ィエD2[Fe(CN)ィイD26ィエD2]X是通过FeィイD1IIIィエD1-CN-NiィイD1IIィエD1键延伸而成的方形片状结构。铁磁相互作用在薄片内运行。整体的磁性由片间分离决定：小的片间分离(&lt；10Å)由于片间反铁磁相互作用而产生亚磁体，而大的片间分离(&gt；10Å)提供铁磁体。片间分离可以通过选择反离子和水合水来控制。2)合成了[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D_1-ィエD_1，CIOィイD_24ィエD_2ィイD_1-ィエD_1)。它们具有各向同性的立方网络，角部有Fe离子和Ni…磁性研究表明，最近的Ni离子之间通过抗磁性的Fe离子发生铁磁相互作用。3)得到了双金属组装[(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，它具有缺陷立方结构，七个角有三个铬原子，四个原子，八个铬-碳-锰边。根据磁化强度(FCM，ZFCM，Rm)和磁滞回线研究，发现它是一个在69K以下表现出磁有序的亚铁磁体。据我们所知，在结构表征的分子基磁中，T_c是最高的。研究了二氮配体桥联的双核铜ィイD1IIィエD1配合物的磁性。基于潜在桥联N-N单键片段，研究了三种多齿双氮配体的双核铜ィイD1IIィエD1配合物的磁性。两个铜ィイD1IIィエD1离子之间的磁相互作用明显地依赖于两个铜生色团相对于N-N键的扭转角。一般来说，较大的畸变角导致没有自旋耦合，较小的畸变角导致较强的反铁磁相互作用。磁性材料的新策略合成了一种新的含有草酰胺和乙醛的桥联配体(HィイD24ィエD2L)。原位合成了其铜ィイD1IIィエD1配合物[Cu(HL)]ィイD1-ィエD1，并与第二个MィイD1IIィエD1离子反应，得到了三核铜ィイD1IIィエD1-MィイD1IIィエD1-铜ィイD1IIィエD1配合物[M{Cu(HL)}ィイD22ィエD2(Dmf)ィイD22ィエD2]/2dmf(M=Mn，Co，Ni，Zn)。[Cu(HL)]ィイd1-ィエd1实体与氢键的N-O-H-N-O络合物形成平面{CunィイD24ィエD2}发色团。两个{Cu(HL)ィイD22ィエD2ィイd1-ィエd1分子与MィイD1IIィエd1离子配位形成八面体构型。[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在K-ィイD_1+ィエD_1和18-冠-O-ィエD_(26)D_2存在下与Mn-ィエD_1+ィイD_1和18-冠-O-ィエD_2反应，得到了一个有序体系，在5.5K下表现出自发磁化。较少

项目成果

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）。

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，

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）。

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.