Exploration of New Stable Neutral Radicals Based on Phenalenyl

基于苯酚基的新型稳定中性自由基的探索

• 批准号: 14340198
• 负责人: NAKASUJI Kazuhiro
• 金额: $ 9.15万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14340198/
• 关键词: neutral radical; odd alternant hydrocarbon; ESR; spin density; spin polarization; crystal structure; topology; phenalenyl; ヘテロラジカル; サーモクロミズム; 機能性材料; 熱励起三重項; 磁化率

Design and synthesis of new stable open-shell molecular systems can contribute the development not only for fundamental spin chemistry but also for exploration of spin-mediated new molecular functionalities. Recently, we succeeded in the stabilization and isolation of the new derivative of phenalenyl which is an odd-alternant hydrocarbon with high symmetry, D3h, by introducing tert-butyl groups at three β positions. In this scientific research, we have further designed new stable neutral radicals based on the phenalenyl with tert-butyl groups as stabilization substituents and synthesized new neutral radicals as follows: 1)2, 5, 8-tri-t-butyl-l, 3-diazaphenalenyl which possesses isoelectronic spin structure with phanalenyl and show the heteroatom effect on spin distribution and thermochromism, 2)2, 5-di-t-butyl-6-oxophenalenoxyl derivatives which show a remarkable change in topological symmetry of the π-electron via heteroatomic perturbation such as the delocalization nature of the introduced oxygen atoms, 3)2, 5, 8-tri-t-butyl-4-oxophenalenoxyl whose π-conjugation network in phenalenyl radical is extended to control the spin density distribution topologically, 4)2, 5-di-t-butyl-6-oxophenalenoxyl derivatives which demonstrate the crystal engineering in magnetic interactions phenalenyl-based spin-delocalized neutral π-radicals by electronic and steric effects.

设计和合成新的稳定的开壳层分子体系不仅有助于基础自旋化学的发展，而且有助于探索自旋介导的新分子功能。最近，我们通过在三个β位上引入叔丁基，成功地稳定和分离了一种具有高对称性的奇交替烃--非那烯基衍生物D3 h。在本科研中，我们进一步设计了以叔丁基为稳定取代基的非那烯基为基础的新型稳定中性自由基，合成了如下新型中性自由基：1）2，5，8-三叔丁基-1，3-二氮杂菲那烯基，其具有与菲那烯基的等电子自旋结构并且显示出对自旋分布和热色性的杂原子效应，5-二叔丁基-6-氧代苯并烯氧基衍生物，其通过杂原子微扰如引入的氧原子的离域性质显示出π电子拓扑对称性的显著变化，3）2，5，8-三叔丁基-4-氧代菲那烯氧基，其菲那烯基中的π共轭网络被扩展以拓扑地控制自旋密度分布，4）2，5-二叔丁基-6-氧代苯并萘氧基衍生物通过电子效应和空间位阻效应证明了磁性相互作用中的晶体工程，苯并萘基自旋离域中性π-自由基。

项目成果

Y.Morita, T.Aoki, K.Fukui, S.Nakazawa, K.Tamaki, S.Suzuki, A.Fuyuhiro, K.Yamamoto, K.Sato, D.Shiomi, A.Naito, T.Takui, K.Nakasuji: "A New Trend in Phenalenyl Chemistry: A Persistent Neutral Radical, 2, 5, 8-Tri-tert-butyl-l, 3-Diaza-phenalenyl, and the Ex

Y.Morita、T.Aoki、K.Fukui、S.Nakazawa、K.Tamaki、S.Suzuki、A.Fuyuhiro、K.Yamamoto、K.Sato、D.Shiomi、A.Naito、T.Takui、K.

Y.Morita, E.Miyazaki, J.Kawai, K.Sato, D.Shiomi, T.Takui, K.Nakasuji: "Syntheses and Spin Structures of 1, 6-Dithiapyrene Derivatives having Iminonitroxide or Oxoverdazyl Moieties."Polyhedron. 22. 2219-2225 (2003)

Y.Morita、E.Miyazaki、J.Kawai、K.Sato、D.Shiomi、T.Takui、K.Nakasuji：“具有亚氨基硝基氧化物或 Oxoverdazyl 部分的 1, 6-二硫芘衍生物的合成和自旋结构。”多面体。

Y.Morita: "ESR/ENDOR Study for New Radical Dianion Species of 6-Oxophenalenoxyl Derivative."In EPR in the 21st Century : Basics and Applications to Material, Life, and Earth Sciences Kawamori, A., Yamauchi, J., Ohta, H., Eds. Elsevier. 384-388 (2002)

Y.Morita：“6-Oxophenalenoxyl 衍生物的新自由基双阴离子物种的 ESR/ENDOR 研究。”21 世纪的 EPR：材料、生命和地球科学的基础知识和应用 Kawamori, A.、Yamauchi, J.、Ohta

Y.Morita: "Synthesis of New 2,7-Diiodo-1,6-dithiapyrene and Crystal Structures of Its Charge-Transfer Salts."Mol.Cryst.Liq.Cryst.. 379. 77-82 (2002)

Y.Morita：“新型 2,7-二碘-1,6-二硫芘的合成及其电荷转移盐的晶体结构。”Mol.Cryst.Liq.Cryst.. 379. 77-82 (2002)

K.Fukui, J.Inoue, T.Kubo, K.Sato, D.Shiomi, Takui, T.Aoki, Y.Morita, K.Yamamoto, K.Nakasuji: "ESR/^1H-ENDOR(TRIPLE) Studies on Generation and Decay Processes of a Triangulene Derivative, The First Non-Kekule Polynuclear Aromatic Hydrocarbon."Magnetic Reso

K.Fukui、J.Inoue、T.Kubo、K.Sato、D.Shiomi、Takui、T.Aoki、Y.Morita、K.Yamamoto、K.Nakasuji：“ESR/^1H-ENDOR(TRIPLE) 研究