Metal Complexes in Extended Systems : Design and Magnetism

1. 通过 M-Cn-M' 连接扩展的双金属磁性材料1) 二维双金属化合物 [Fe(Cn)D26D2] 在硬币处与 Fe 离子连接，在边缘处与 Ni 离子连接。铁磁相互作用在片材内起作用。整体磁性由片间间距控制：小片间间距（<10 Å）由于片间反铁磁相互作用而产生超磁体，而大片间间距（>10 Å）则提供铁磁体。片间分离可以通过选择抗衡离子和水合水来控制。2) 3 维双金属组件 [Ni(L)D22D2]D23D2[FeD1IID1(CN)D26D2]XD22D2 (L=en, tn; X=PFD26D2D1-D1, CIO-D24-D2-D1-D1) 已制备并结构特点。它们具有各向同性的立方网络，角上有 Fe 离子，边缘上有 Ni 离子。磁性研究表明，最近的 Ni 离子与反磁性 Fe 离子之间存在铁磁相互作用。3) 获得了双金属组件 [(Mn)en]D23D2[Cr(CN)D26D2]D22D2 4HD22D2O，其具有缺陷的立方结构，在七个角和八个角处具有三个 Cr 原子和四个原子。 Cr-CN-Mn 边缘。基于磁化强度（FCM、ZFCM、RM）和磁滞研究，发现它是一种磁序低于69 K的亚铁磁体。据我们所知，其Tc是结构表征的分子磁体中最高的。2．二嗪配体桥接的双核 CuiD1IID1 配合物的磁性研究了基于潜在桥接 N-N 单键片段的三个多齿二嗪配体的双核 CuiD1IIiD1 配合物。两个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。一般来说，大的畸变角不会产生自旋耦合，小畸变会产生强的反铁磁相互作用。3．磁性材料的新策略制备了具有草酰胺基和乙醛酸酯基团（D2L）的新桥配体。原位合成其CuD1IID1配合物[Cu(HL)]D1-D1，并与第二个D1IID1离子反应，得到三核D1-D1D1-D1D1配合物[M{Cu(HL)}D22D2(dmf)D22D2]/2dmf(M=Mn、Co、Ni、Zn)。 [Cu(HL)]D1-D1 实体与氢键 N-O-H-N-O 螯合物形成平面 {CuND24D2} 发色团。两个 {Cu(HL)D22D2D1-D1 分子与 MD1IID1 离子配位，与两个 dmf 分子一起提供八面体几何形状。 [Mn{Cu(Hl)}]D22D2(dmf)D2·2(dmf)D22D2}2dmf 在 KD1 和 18-crown-OD26D2 存在下与 MnD1IID1 离子反应，提供在 5.5 K 下表现出自发磁化的有序系统。这项工作说明了使用设计的桥接配体逐步合成双金属磁体。较少的

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