Development of Molecule-Based Magnets Tunable by Means of Supramolecular Chemistry

开发可通过超分子化学调节的分子磁体

• 批准号: 13640575
• 负责人: ISHIDA Takayuki
• 金额: $ 2.3万
• 依托单位: The University of Electro-Communications
• 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 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13640575/
• 关键词: Molecule-based magnets; metal-assembled complex; Supramolecular chemistry; Porous materials; Weak ferromagnet; ピリミジン; 有機ラジカル; 有機強磁性体; 磁気的相転移; ホストゲスト化学; 結晶工学

Supramolecular techniques such as host-guest complex formation have been used to tune molecule-based magnetic materials. We have developed two nano-porous magnetic materials, whose magnetic properties were changed by inclusion of small diamagnetic molecules.The first are low-temperature magnets derived from iron(II), dicyanamide anion, and pyrimidine, which have guest molecules incorporated in the clearance of the 3-D framework. The T_c ranges from 3.4 K to 5.6 K, depending on the guest molecules. They are characterized as canted antiferromagnets below T_c. The critical temperature, critical field, and spontaneous magnetization are Modulated by the guest inclusion.The second are hexanuclear wheel-shaped copper(II) complexes, whose crystals have a channel structure in a direction perpendicular to the molecular plane. The ferromagnetic interaction, which is ascribed to intermolecular contacts between the radical substituents, was remarkably enhanced by guest inclusion within a channel. The effect of water is especially noticeable ; the magnetic properties returned to the empty one by removal of water. This system is a rare example of realizing the regulation of magnetic properties by means of host-guest chemistry.We also prepared metal-radical hybrid magnets using bridging ligands as supramolecular synthons. Novel paramagnetic chelating ligands (4ImNNH, pzNN, pzIN, pzbisNN, and pzbisIN) were developed and applied to the synthesis of mononuclear, triangular, and linear polynuclear complexes. We have exploited potential utility of the smallest bridging paramagnetic ligands (HIN and HNN) and clarified that the choice of small ligands was a promising strategy to bestow strong exchange interaction in metal-radical solids.

超分子技术（例如宿主 - 温复合物形成）已用于调整基于分子的磁性材料。我们已经开发了两种纳米磁性磁性材料，它们的磁性特性是通过包含小的二磁分子而改变的。第一个是源自铁（II），二氯酰胺阴离子和嘧啶的低温磁体，它们的客体分子掺入了3-D框架清除中。 T_C的范围从3.4 K到5.6 K，具体取决于来宾分子。它们的特征是T_C以下的倾斜抗fiferromagnet。临界温度，临界场和自发磁化强度通过客人包容调节。第二个是六核轮状铜（II）配合物，其晶体在垂直于分子平面的方向上具有通道结构。铁磁相互作用归因于自由基取代基之间的分子间接触，通过在通道内的来宾包含来显着增强。水的影响特别明显。磁性特性通过去除水返回到空的。该系统是通过宿主 - 吉斯特化学实现磁性特性的罕见例子。我们还使用桥接配体作为超分子合成子制备了金属激进的杂种磁铁。开发了新型的顺磁性螯合配体（4IMNNH，PZNN，PZNN，PZBISNN和PZBISIN），并应用于单核，三角形和线性多核复合物的合成。我们利用了最小的桥接顺磁配体（HIN和HNN）的潜在效用，并澄清说，小体配体的选择是赋予金属 - 激进固体中强交换相互作用的一种有希望的策略。

项目成果

M.Yasui, 他4名: "Bis(hfac)-Copper(ll)Complexes Bridged by Pyrimidines Showing Magnetic Interactions"Acta Crystallographica Section B. 57. 772-779 (2001)

M. Yasui 和其他 4 人：“Bis(hfac)-Copper(ll)Complexes Bridged by Pyrimidines Showing Magnetic Interactions” Acta Crystallographa 第 B. 57. 772-779 (2001)

T.Matsuyama 他3名: "Hybrid Magnetic Solids of Radical-Substituted Heteroaromatic Compounds with Metal Halides"Synthetic Metals. (印刷中). (2003)

T. Matsuyama 和其他 3 人：“自由基取代的杂芳族化合物与金属卤化物的混合磁性固体”合成金属（2003 年）。

G.Kurokawa, M.Sekii, T.Ishida, T.Nogami: "Crystal Structure of a Molecular Complex from Native β-Cyclodextrin and Copper(II) Chloride"Supramol.Chem.. (in press). (2004)

G.Kurokawa、M.Sekii、T.Ishida、T.Nogami：“天然 β-环糊精和氯化铜 (II) 的分子复合物的晶体结构”Supramol.Chem..（出版中）。

T.Ishida 他2名: "Host-guest chemistry of radical-copper wheels. A supramolecular control of magnetic exchange coupling"Polyhedron. 22. 2133-2138 (2003)

T. Ishida 和其他 2 人：“自由基铜轮的主客体化学。磁交换耦合的超分子控制”Polyhedron 22. 2133-2138 (2003)。

M.Seino, Y.Akui, T.Ishida, T.Nogami: "Magnetic Properties of 9,9-Disubstituted 9,10-Dihydroacridine-10-yloxyls"Synth.Met.. 133-134. 581-583 (2003)

M.Seino、Y.Akui、T.Ishida、T.Nogami：“9,9-二取代的 9,10-二氢吖啶-10-yloxyls 的磁性”Synth.Met.. 133-134。