Generation of radical ions of pyrazolines and construction of an electron transfer system.

吡唑啉自由基离子的产生和电子转移系统的构建。

• 批准号: 16550162
• 负责人: KITAMURA Akihide
• 金额: $ 2.3万
• 依托单位: Chiba University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16550162/
• 关键词: Photochemistry; Organic Chemistry; Photochemical Property; Photoswitch; Nano Materical; イオンラジカル; 電子伝達; 光誘起電子移動; アゾ化合物

Radical cations generated from cyclic azoalkanes by photoinduced electron transfer (PET) have recently been investigated and produced a few characteristic compounds by rearrangements and solvent additions. The reaction mechanisms become complex when the generated radical cations have the possibility of rearranging due to their geometric constraints and stabilities, as these species appear to be involved in denitrogenation. In our previous studies using the 1-pyrazolines and 9,10-dicyanoanthracene (DCA) as an electron accepting sensitizer, the PET reaction was found to cause aryl migration involving the radical cation intermediates. In spite of the fact that the behavior of the nitrogen-retained radical cations are of considerable interest, nitrogen-retained products by the PET reaction have not been obtained, and the products are nitrogen-eliminated compounds. In this project, we report the first example of the use of cyclic azoalkanes for the PET reaction in which nitrogen-retained products are obtained from the radical cation species of 3-alkylidene-1-pyrazolines having an exocyclic double bond, and that the successful detection of the nitrogen-retained radical cations was accomplished by a laser flash photolysis (LFP) technique.

最近已经研究了由光诱导的电子传递（PET）产生的自由基阳离子，并通过重排和溶剂添加产生了一些特征化合物。当产生的自由基阳离子由于其几何约束和稳定性而有可能重新排列时，反应机制变得复杂，因为这些物种似乎参与了硝化作用。在我们以前使用1-吡唑啉和9,10-二烷那烷（DCA）作为电子接受敏化剂的研究中，发现PET反应会导致涉及自由基阳离子中间体的芳基迁移。尽管事实是，氮的自由基阳离子的行为具有很大的兴趣，但尚未获得宠物反应的氮腐烂产物，并且产物是氮溶解的化合物。在该项目中，我们报告了使用环状偶氮烷烃进行PET反应的第一个例子，在该反应中，从氮阳离子的三烷基1-吡唑啉的激进阳离子物种中获得了具有外孢酸双键的激进阳离子物种，并且成功地检测了氮的自由基阳离子的成功检测是通过LASER SEDISP（lfppphpppppp）。

项目成果

Dye-Assissted Structural Modulation of Hydrogen-Bonded Binary Supramolecular Polymers.

氢键二元超分子聚合物的染料辅助结构调制。

• 发表时间: 2005
• 期刊: Chemistry of Materials Vol.17, No.17
• 作者: S.Yagai;M.Higashi;T.Karatsu;A.Kitamura
• 通讯作者: A.Kitamura

Hierarchical organization of photoresponsive hydrogen-bonded rosettes

• DOI: 10.1021/ja052645a
• 发表时间: 2005-08-10
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Yagai, S;Nakajima, T;Kitamura, A
• 通讯作者: Kitamura, A

Phototriggered self-assembly of hydrogen-bonded rosette.

• DOI: 10.1021/ja047783z
• 发表时间: 2004-08
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: S. Yagai;T. Nakajima;T. Karatsu;K. Saitow;Akihide Kitamura

Dye-Assissted Structural Modulation of Hydrogen-Bonded Binary Supramolecular Polymers

氢键二元超分子聚合物的染料辅助结构调制

• 发表时间: 2005
• 期刊: Chemistry of Materials 17・17
• 作者: Shiki Yagai

Generation and reactions of 3-alkylidene-1-pyrazoline radical cations by photoinduced electron transfer.

光诱导电子转移产生 3-亚烷基-1-吡唑啉自由基阳离子的生成和反应。

• 发表时间: 2005
• 期刊: Tetrahedron Letters Vol.46,No.2
• 作者: Takashi Karatsu;Yoshinori Miyazaki;Yuuki;Shimura;Akinori Okayasu;Takaaki Suzuki;Masaki Higashi;Shiki Yagai;Kitamura Kitamura
• 通讯作者: Kitamura Kitamura