Construction of Nanosize Magnetic Bar by Assembling of Organic Molecules and Control of Their Arrangement

有机分子组装构建纳米磁棒及其排列控制

• 批准号: 15310094
• 负责人: YOSHIOKA Naoki
• 金额: $ 3.39万
• 依托单位: KEIO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-15310094/
• 关键词: Molecule-Based Magnet; Stable Organic Radical; Branched Hydrogen Bond; Ferromagnetism; Magneto-Structural Correlation; Piled Columnar Structure; Nitroxy Radical; Nanosize Magnet; 分子強磁性体; 水素結合; 低次元磁性; ニトロキシルラジカル; 有機ラジカル; 連鎖形成; ニトロキシドラジカル

Recently, there has been substantial interest in the study of molecular-based magnetism. Whereas these ferromagnetic orderings have been discovered fortuitously, methodology for designing intermolecular exchange coupling pathways has not been established yet. Organic ferromagnets so far reported have suitable arrangements to fulfill the model proposed by McConnell and/or orbital orthogonality ; however, the control of molecular arrangement in the crystal does not necessarily correspond to predictable strategy. Whereas molecular chemistry deals with the design and the synthesis of individual radical units, their assembly into a solid is governed by concepts of supramolecular chemistry. Our ultimate objective is to design radical molecules whose assembled structure can be predicted from their chemical structure.We have already found the formation of magnetic self-assemblies in nitronyl nitroxyl (4,4,5,5-tetramethyl-4,5-dihydro-1 H-imidazoline-1 oxyl-3-oxide) derivatives carrying heterocycles with the NH site, such as the imidazol-2-yl, benzimidazol-2-yl, naphth[2,3-d]imidazol-2-yl and azaindol-2-yl rings. Among these compounds, the benzimidazole derivatives formed a piled columnar assembly induced by intra- and intermolecular hydrogen bondings between an NH site and two nitroxyl O atoms. The assembly exhibited a 1D ferromagnetic chain behavior (J=ca.13〜16 cm^<-1>) that could be rationalized by through space close contact between the singly occupied molecular orbitals (SOMOs).To enhance the magnetic interaction in molecular systems, it is favorable to design multipoint close contacts between the SOMOs, because intermolecular magnetic interaction is described by the sum of the spin-density product of nearby atoms belonging to neighboring molecules. We also focused on 2,2-diphenyl-1,2-dihydroquinoline-1-oxyl and found several interesting magnetic characteristics in chemically modified derivatives.

最近，对基于分子的磁性的研究引起了极大的兴趣。尽管这些铁磁秩序已经被发现了，但尚未建立设计分子间交换耦合途径的方法。到目前为止，有机铁磁体已有适当的安排来满足麦康奈尔和/或轨道正交性提出的模型；但是，晶体中分子排列的控制不一定与可预测的策略相对应。分子化学涉及单个自由基单元的设计和合成，而它们的组装成固体则由超分子化学的概念控制。我们的最终目标是设计根部分子，可以从其化学结构中预测其组装结构。我们已经在硝基硝基硝氧基（4,4,4,5,5-四甲基-4,5-二甲基-1-5-二甲基-1 H-米咪唑啉-1 oxylazoline-oxyl-oxyl-oxyl-oxylive）中均与携带的hyderocycycycy nh y骨相处，在硝基硝基硝基（4,4,4,5,5-四甲基-4,5-甲基-4,5-二甲基-4,5-二甲基-4,5-二甲基-4,5-二甲基-4,5-二甲基-1）中形成磁性，咪多唑-2-基，苯咪唑-2-基，萘[2,3-D]咪唑-2-基和偶氮二醇-2-基环。在这些化合物中，苯唑唑衍生物形成了由NH位点和两个硝基氧基O原子之间的分子内和分子间氢键诱导的桩柱组件。组装暴露了1D铁磁链行为（J = Ca.13-16 cm^<-1>>）可以通过通过空间密切接触在单一占据的分子轨道（SOMOS）之间进行合理化的，以增强分子系统中的磁相互作用，以增强分子系统的磁性相互作用，因为它可以通过相互作用的相互作用，因为它相互互动，因为它们相互作用的磁性相互作用，因为它们相互作用是对数值的相互作用，并且是对线性的相互作用的，并且是对磁性的相互作用，并且是对数的相互作用的相互作用。相邻分子。我们还专注于2,2-二苯基-1,2-二氢喹啉-1-氧基，并在化学改性的衍生物中发现了几种有趣的磁性特征。

项目成果

ニトロニルニトロキシド有機固体における磁気的相互作用-水素結合を用いたアプローチ-

硝基硝基氧有机固体中的磁相互作用 - 使用氢键的方法 -

• 发表时间: 2004
• 期刊: 日本結晶学会誌 46
• 作者: D.Matsunaga;H.Asanuma;M.Komiyama;M.Yao;M.Yao;H.Nagashima;長島英明
• 通讯作者: 長島英明

H.Nagashima: "Metamagnetic behavior observed in purely organic 5-azaindol-2-yl nitronyl nitroxide brick-wall architecture"Crystal Growth & Design. Vol.4 No.1. 19-21 (2004)

H.Nagashima：“在纯有机 5-氮杂吲哚-2-基硝基硝基氧砖墙结构中观察到的变磁行为”晶体生长

H.Nagashima: "Coexistence of an antiferromagnetically coupled dimer and isolated paramagnetic spin in 4-azaindol-2-yl nitronyl nitroxide crystal"New Journal of Chemistry. Vol.27 No.5. 805-810 (2003)

H.Nagashima：“4-氮杂吲哚-2-基硝基硝基氧晶体中反铁磁耦合二聚体和孤立顺磁自旋的共存”《新化学杂志》。

Theoretical Study on Magnetic Properties of Imidazolyl Nitronyl Nitroxide Derivatives

咪唑基硝基氮氧化物衍生物磁性能的理论研究

• 发表时间: 2003
• 期刊: Synthetic Metals 137(1-3)
• 作者: Masaru Yao;Masaru Yao;Masaru Yao;Masaru Yao;Masaru Yao;Masaru Yao;Masaru Yao;M.Yao;H.Taima;M.Yao;M.Yao;M.Yao;M.Yao;Hideaki Nagashima;Hideaki Nagashima;長島 英明;Hideaki Nagashima;Hideaki Nagashima;H.Nagashima;長島英明;Masaru Yao;Hideaki Nagashima;Hideaki Nagashima;Hideaki Nagashima;Masaru Yao;Masaru Yao;Hideaki Nagashima
• 通讯作者: Hideaki Nagashima

Amphiphilic meso-Disubstituted Porphyrins : Synthesis and the Effect of the Hydrophilic Group on Absorption Spectra at the Air-Water Interface

两亲性内消旋二取代卟啉：合成及其亲水基团对空气-水界面吸收光谱的影响

• 发表时间: 2005
• 期刊: Langmuir 21
• 作者: K.Ohkawa;M.Yao
• 通讯作者: M.Yao