DISIGN AND CONSTRUCTION OF ORGANIC FERROMAGNET AND THEIR CRYSTAL DESIGN.

有机铁磁体及其晶体设计的设计和构造。

• 批准号: 06453037
• 负责人: NAKAMURA Nobuo
• 金额: $ 3.84万
• 依托单位: HOSEI UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06453037/
• 关键词: hexacarbene; nonacarbene; ethynyl ketone; phenylnitronyl nitroxide; naphthylnitronyl nitroxide; ferromagnetic interaction; x-ray crystallography; no-bond atomic distance; 環状ヘキサケトン; 環状オクタケトン; 環状ヘキサカルベン; ナフチルアミンN-オキシル; トリフェニレン; ポリカルベン; 有機強磁性体

In order to achieve an organic ferromagnet, two approaches to it were adopted ; (i) intrarmolecular approach and (ii) intermolecular one.(i) Previous ESR studies on branched-chain hexa-and nonacarbenes, successfully generated photochemically at a cryogenic temperature from the corresponding diazo precursors, suggested their magnetic behaviors as spin-glass or super-paramagnetic. Though large scale preparations of the carbene precursors were carried out to get further insights into the phenomenon, preliminary experiments on an AC-SQUID instrument revealed that the instrumental sensitivity was quite disappointing under an extremely dilute condition which was definitely required for the carbene not to interact antiferromagnetically.The key step for the preparation of those carbene precursors was an amine-catalyzed cyclo-trimerization reaction of ethynyl ketones, whose mechanisms were determined by the use of substituted aryl ethynyl ketones to involve aryl 2-aminoethenyl ketones.Cyclic he … More xacarbene which might be assumed to have a partial skeleton of an ideal polycarbene with honycomb structure was successfully generated to show that the spin quantum number S is 6 as expected theoretically. This result together with those of isomeric branched-chain hexacarbenes clearly demonstrates that the spin multiplicity of the alternant hydrocarbon molecules is determined by the topological symmetry of the pi-bond sequence.(ii) As preliminary X-ray structural analysis on (3,5-dihydroxyphenyl) nitronyl nitroxide indicated the hydroxyl group to be effective in arranging the molecules two dimentionally, syntheses, magnetic observations, and x-ray crystallographic analyzes of several (hydroxynaphthyl) nitronyl nitroxide isomers were performed along with those of the corresponding (bromophenyl)- and (bromonaphthyl) nitronyl nitroxide radicals. It was found that some of these radicals showed ferromagnetic behaviors at extreme low temperatures. Further studies on these molecules are under way. Less

为了获得有机的铁磁铁，采用了两种方法；在极度稀释状态下，卡宾人的敏感性在themononn n strumental的敏感性中被刺激了，carbene的前体被定义为无抗抗性的一步。通过使用取代的Arynyl酮在芳基2-氨基乙烯基酮的芳基。CyclicHe ...与honycomb结构的理想聚苯乙烯的更多leton成功地生成了自旋量子数S，如预期的是6，这与理论上的结果是6分支链六边形。发现其中一些自由基对分子的进一步研究较少

项目成果

Nobuo Nakamura, Yasuharu Tanabe, Takayuki Ooe, Katsuya Inoue, and Hiizu Iwamura: "Syntheses and Magnetic Behaviors of Substituted 1- and 2-Naphthylnitrony1 Nitroxides." (to be published.).

Nobuo Nakamura、Yasuharu Tanabe、Takayuki Ooe、Katsuya Inoue 和 Hiizu Iwamura：“取代的 1- 和 2-萘基硝基 1 氮氧化物的合成和磁性行为。”

Kenji Matsuda, Nobuo Nakamura, and Hiizu Iwamura: "Exploratory and Mechanistic Studies of the Trimerization Reaction of Benzoylacetylenes in the Presence of a Secondary Amine." Chem.Lett.1765-1768 (1994)

Kenji Matsuda、Nobuo Nakamura 和 Hiizu Iwamura：“仲胺存在下苯甲酰乙炔三聚反应的探索性和机理研究”。

K.Matsuda et al.: "Exploratory and Mechanistic Studies of the Trimerization Reaction of Benzoyl-acetylenes in the Presence of a Secondary Amine." Chem.Lett.,. 1994. 1765-1768 (1994)

K.Matsuda 等人：“仲胺存在下苯甲酰乙炔三聚反应的探索性和机理研究”。

Kenji Matsuda, Nobuo Nakamura, Kazuyuki Takahashi, Katsuya Inoue, Noboru, Koga, and Hiizu Iwamura: "Design, Synthesis, and Characterization of Three Kinds of pi-Cross-Conjugated Hexacarbenes with High-Spin (S=6) Ground States." J.Am.Chem.Soc.117. 5550-556

Kenji Matsuda、Nobuo Nakamura、Kazuyuki Takahashi、Katsuya Inoue、Noboru、Koga 和 Hiizu Iwamura：“三种具有高自旋 (S=6) 基态的 pi 交叉共轭六碳烯的设计、合成和表征。”

N.Nakamura et al.: "Ferromagnetic Interactions in Crystalline 3-Bromophenylnitronyl Nitroxide" (to be published).

N.Nakamura 等人：“结晶 3-溴苯基硝酰基硝基氧化物中的铁磁相互作用”（待出版）。