Precise Molecular Design and Construction of Organic Ferromagnets

有机铁磁体的精确分子设计和构建

基本信息

  • 批准号:
    03102003
  • 负责人:
  • 金额:
    $ 98.56万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for Specially Promoted Research
  • 财政年份:
    1991
  • 资助国家:
    日本
  • 起止时间:
    1991 至 1993
  • 项目状态:
    已结题

项目摘要

1) Synthesis of Super-high-spin Polycarbenes with Starburst Structures : A series of polycarbenes 1,3,5- [H (C_6H_4C : ) n/3] 3C_6H_3 have been synthesized and found from their magnetization data to have unprecedentedly high-spin S=6 and 9 ground states for n=6 and 9, respectively. Having optimized the reaction conditions for the construction of the 1,3,5-trisubstituted central benzene rings, we have made logical extension to more highly branched polycarbenes with higher spin concentration. While some of the polycarbenes showed a superparamagnetic properties due to blocking of the rotation of the principal axis of magnetization, the intermolecular and interbranch interactions were found to be antiferromagnetic.2) Synthesis of Persistent High-spin Polynitroxide Radicals : Two or three nitroxide radical centers were assembled into one molecules by means of ferromagnetic couplers m-C_6H_4 or 1,3,5-C_6H_3. The di-and trinitroxide radicals were found by the analysis of their EPR fine structures and SQUID susceptibility to have triplet and quartet ground states, respectively.3) Construction of Molecular Magnets by Assembling High-spin Molecules : The persistent di-and trinitroxide radicals were used as di-and trivalent ligands for transition metal complexes. In the case of a combination of Mn (hfac) _2 and trinitroxide radicals (TN), molecular magnets with Curie temperatures of 3.4 and 46 K have been obtained. X-ray crystallographic analyzes revealed the layred honey-combed network and three dimensional crossed-parallels structures, respectively, both consisting of units (TN) _2 {Mn (hfac) _2} _3.4) Design and Survey of Intemolecular Interaction Assisting Spin Alignment in Organic Free Radicals in Solid State : Prototypes for the hydrogen bonding interaction in aromatic polyamides and the S...S interaction in polythiophenes have been studied to find the potentiality of these interaction in helping intermolecular spin alignment.
1)具有星爆结构的超高自旋聚碳酸酯的合成:合成了一系列的聚碳酸酯1,3,5- [H (C_6H_4C:) n/3] 3C_6H_3,并从它们的磁化数据中发现,在n=6和9时,它们分别具有前所未有的高自旋S=6和9基态。优化了1,3,5-三取代中心苯环的反应条件,并进行了自旋浓度更高的高支化聚碳的逻辑延伸。某些聚碳化合物由于阻止了磁化主轴的旋转而表现出超顺磁性,而分子间和分支间的相互作用则是反铁磁性的。2)持久性高自旋多氮氧化物自由基的合成:利用铁磁偶联剂m-C_6H_4或1,3,5- c_6h_3将两个或三个氮氧化物自由基中心组装成一个分子。通过分析二氮自由基和三氮自由基的EPR精细结构和SQUID对三态基态和四态基态的敏感性,分别发现了二氮自由基和三氮自由基。3)通过组装高自旋分子构建分子磁体:持久性二氮和三氮自由基被用作过渡金属配合物的二价和三价配体。在Mn (hfac) _2与三硝基(TN)结合的情况下,获得了居里温度分别为3.4 K和46 K的分子磁体。x -射线晶体学分析显示,其结构为层状的蜂窝状网状结构和三维交叉平行结构,均由单元(TN) _2 {Mn (hfac) _2} _3.4组成。研究了多噻吩中的S相互作用,发现了这些相互作用有助于分子间自旋排列的潜力。

项目成果

期刊论文数量(113)
专著数量(0)
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专利数量(0)
中村暢男: "A Branched-Chain Nonacarbene with a Nonadecet Ground State:A Step Nearer to Superparam agnetic Polycarbenes" Angewandte Chemie,Int.Ed.Engl.32. 872-874 (1993)
Nobuo Nakamura:“具有 Nonadecet 基态的支链九碳烯:更接近超参数磁性聚碳烯”Angewandte Chemie,Int.Ed.Engl.32 (1993)。
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菅野文雄: "4,6-Dimethoxy-1,3-phenylenebis(N-tert-butyl nitroxide)with a Singlet Ground State" Jornal of the American Chemical Society. 115. 847-850 (1993)
Fumio Kanno:“具有单线态基态的 4,6-二甲氧基-1,3-亚苯基双(N-叔丁基硝基氧)”美国化学会杂志 115. 847-850 (1993)。
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T.Nogami: "A New Organic Ferromagnet : 4-Benzylideneamino-2,2,6,6-tetramethylpiperidin-1-oxyl" Chem.Lett.1994. 29-32 (1994)
T.Nogami:“一种新的有机铁磁体:4-亚苄基氨基-2,2,6,6-四甲基哌啶-1-氧基”Chem.Lett.1994。
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Andrew S.Ichimura: "Calibration of a Semiempirical Procedure for Predicting the Ground State Spin Multiplicities of Open-shell Molecules. Applications to New Systems" J.Phys.Org.Chem.7. 207-217 (1994)
Andrew S.Ichimura:“用于预测开壳分子基态自旋多重性的半经验程序的校准。在新系统中的应用”J.Phys.Org.Chem.7。
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K.Inoue: "Magnetic Properties of the Crystals of p- (1-Oxyl-3-oxido-4,4,5,5-tetramethyl-2-imidazolin-2-yl) benzoic Acid and Its Alkali Metal Salts" Chem.Phys.Lett.-. 207. 551-554 (1993)
K.Inoue:“对-(1-氧基-3-氧化-4,4,5,5-四甲基-2-咪唑啉-2-基)苯甲酸及其碱金属盐晶体的磁性”化学。
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IWAMURA Hiizu其他文献

IWAMURA Hiizu的其他文献

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{{ truncateString('IWAMURA Hiizu', 18)}}的其他基金

A trial manufacture of irradiation/photometry system for cryogenic magneic susceptometer and optofunctionalization of molecule based magnet
低温磁感受器辐照/测光系统的试制及分子磁体的光功能化
  • 批准号:
    08554023
  • 财政年份:
    1996
  • 资助金额:
    $ 98.56万
  • 项目类别:
    Grant-in-Aid for Scientific Research (A)
Determination of Ground State Spin Multiplicity of Basic non-Kekule Hydrocarbons by Measuring Paramagnetic Susceptibility.
通过测量顺磁化率测定碱性非凯库勒烃的基态自旋多重度。
  • 批准号:
    06453035
  • 财政年份:
    1994
  • 资助金额:
    $ 98.56万
  • 项目类别:
    Grant-in-Aid for General Scientific Research (B)
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