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，人们对分子基磁性的研究产生了浓厚的兴趣。虽然这些铁磁有序已经被偶然发现，但设计分子间交换耦合路径的方法还没有建立起来。到目前为止，已报道的有机铁磁体具有合适的排列方式来满足McConnell提出的模型和/或轨道正交性；然而，控制晶体中的分子排列并不一定对应于可预测的策略。虽然分子化学涉及单个自由基单元的设计和合成，但它们组装成固体是由超分子化学的概念支配的。我们的最终目标是设计能够通过化学结构预测其组装结构的自由基分子。我们已经在硝基氮氧基(4，4，5-四甲基-4，5-二氢-1H-咪唑啉-1氧基-3-氧化物)衍生物中发现了磁性自组装的形成，例如咪唑-2-基，苯并咪唑-2-基，环[2，3-d]咪唑-2-基和氮杂环-2-基。在这些化合物中，苯并咪唑类化合物通过NH位和两个氮氧基氧原子之间的分子内和分子间氢键形成堆积的柱状组装。该体系表现出一维铁磁链行为(J=约13~16 cm^&lt；-1&gt；)，可通过单占据分子轨道(SomOS)之间的空间紧密接触来合理化。为了增强分子体系中的磁性相互作用，分子间磁性相互作用可用邻近原子的自旋密度积之和来描述。我们还对2，2-二苯基-1，2-二氢喹啉-1-氧基进行了研究，发现在化学修饰的衍生物中有一些有趣的磁性特征。

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

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

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》。

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