Construction of Local Spin Ordering System through Polarons

通过Polarons构建局部自旋排序系统

• 批准号: 09440237
• 负责人: SUGAWARA Tadashi
• 金额: $ 3.2万
• 依托单位: THE UNIVERSITY OF TOKYO
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09440237/
• 关键词: nitronyl nitroxide; ploypyrrole; ESR; triplet; exchange interaction

Construction of high spin molecules is an important target of research in molecular magnetism'. We have demonstrated a number of high spin polycarbenes based on the pi-topology. However there is a problem concerning the kinetic stability of high spin polycarbenes. The aim of this project is to prepare stable high spin molecules, replacing a siguma-spin and a pi-spin of carbenes with a local spin of the stable radical unit and a polaronic spin in the conjugated pi-system. As a target molecule we designed a polypyrrole carrying nitronyl nitroxide groups. A ferromagnetic coupling of the oligomers is originated from a space-sharing nature of the partial molecular orbitals belonging to the radical unit and the pyrrole unit. As an appropriate building block of such a high spin oligopyrrole, we prepared several pyrrole derivatives and found that N-(p-NN-phenyl)pyrrole affords a ground state triplet species upon one-electron oxidation. Furthermore, thienyl groups were introduced at the alpha-positions on both sides of the pyrrole ring as reactive sites. This monomer turned out to afford desired hybrid-oligomers under the oxidative condition. Magnetic and conductive properties of them will be investigated even after the research period of this project.

高自旋分子的构建是分子磁学研究的重要目标。我们已经证明了一些高自旋聚卡宾的基础上的π-拓扑结构。然而，存在关于高自旋聚卡宾的动力学稳定性的问题。该项目的目的是制备稳定的高自旋分子，用稳定自由基单元的局部自旋和共轭π系统中的极化子自旋取代卡宾的σ自旋和π自旋。作为目标分子，我们设计了一个带有硝酰基氮氧自由基的聚吡咯。低聚物的铁磁耦合源于属于自由基单元和吡咯单元的部分分子轨道的空间共享性质。作为这样的高自旋寡吡咯的适当的构建块，我们制备了几个吡咯衍生物，并发现N-（p-NN-苯基）吡咯提供一个基态三重态物种后，单电子氧化。此外，在吡咯环两侧的α-位上引入噻吩基作为反应位点。该单体在氧化条件下得到所需的混合低聚物。即使在本项目的研究期结束后，也将对它们的磁性和导电性进行研究。

项目成果

T.Sugawara: ""Chemical Transformation"in Functionality of Moleculer System I" Springer-Verlag,Tokyo Ed.S.Nagakura,K.Honda, 21 (1997)

T.Sukawara：“分子系统 I 功能中的“化学转化”” Springer-Verlag，东京 Ed.S.Nagakura，K.Honda，21 (1997)

G.Ono et al.: "Structure and physical properties of a hydrogen-bonded self-assembled material composed of a carbamoylmethyl substituted TTF derivative" J.Mater.Chem.8. 1703-1709 (1998)

G.Ono等人：“由氨基甲酰甲基取代的TTF衍生物组成的氢键自组装材料的结构和物理性质”J.Mater.Chem.8。

A.Sasaki 他3名: "Chemical Consequences of Arylnitrenes in the Crystalline Environment" Bull.Chem.Soc.Jpn.71. 1259-1275 (1998)

A.Sasaki 和其他 3 人：“结晶环境中芳基氮烯的化学后果”Bull.Chem.Soc.Jpn.71 (1998)。

T.Matsuo 他5名: "Calorimetric Study of Proton Tunneling in Solid 5-Bromo-9-Hydrozyphenalenone and Deuteration-Induced Phase Transitions Its Deuteroxy Analog" J.Chem.Phys.108(23). 9809-9816 (1998)

T.Matsuo 和其他 5 人：“固体 5-Bromo-9-Hydrozyphenalenone 中质子隧道效应及其氘代类似物的量热研究”J.Chem.Phys.108(23) (1998)。

菅原 正, 泉岡 明: "日本化学会編,学会出版センター" 有機導電体の設計と合成 化学総説「π電子系有機固体」, 3-20 (1998)

菅原正、井冈彰：《日本化学会、学会出版中心编》有机导体的设计与合成，化学评论《π电子基有机固体》，3-20（1998）