Design of Multi-center Multi-step Multi-redox Organic and Metallic Hybrid Molecules

多中心多步多氧化还原有机金属杂化分子的设计

• 批准号: 15550023
• 负责人: OGAWA Satoshi
• 金额: $ 2.37万
• 依托单位: Iwate University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550023/
• 关键词: Heteroatom; Metallacycle; Metallocene; 5-Membered heterocycles; 7π-Electron system; Organic-metallic Hybrid; Redox system; Electron transfer system

In recent years, the study of molecules comprising multiple reduction-oxidation (redox) centers have attracted considerable research interest in the field of material science due to the preparation of new π-conjugated materials with application in material science. Moreover, this kind of molecule having more than two redox-active metal centers is a fundamentally attractive target for the study of multi-electron transfer processes via the mixed valence state derived from these multi-metallic systems. On the other hand, interest in the design of novel redox-active organic centers by the use of a 5π- and 7π-electron framework containing group 16 elements has led us to explore the synthesis of new 5-membered heterocycles containing sulfur and/or selenium atom(s). Therefore, we have designed 2,3-disubstituted benzo[b]thiophene and 1,3-disubstituted benzo[c]chalcogenophene as both cathodic and anodic multiple-redox active organic-organometallic hybrid molecules. 2,3-Disubstituted benzo[b]thi … More ophenes, 1,3-disubstituted benzo[c]thiophenes, and 1,3-disubstituted benzo[c]selenophene have been systematically and selectively synthesized from benzo[b]thiophene or phthaloyl dichloride as a starting material, respectively. Characterization of the molecules was performed by physical and spectroscopic means and X-ray crystallographic analyses. The cyclic voltammograms of the chalcogenophene derivatives containing aryl fragments showed well-defined reversible both anodic and cathodic steps derived from the unusually stable 5π chalcogenophene radical cations and 7π chalcogenophene radical anions. The cyclic voltammograms of the novel chalcogenophene derivatives containing ferrocenyl fragments showed a well-defined reversible cathodic step derived from the unusually stable 7π chalcogenophene radical anions and two distinct reversible anodic steps derived from ferrocenium cations separated from each other by a thiophene-heterocycle. The radical character of several novel 7π chalcogenophene radical anions was measured by ESR spectroscopy. Less

近年来，由于新型π共轭材料的制备及其在材料科学中的应用，包含多个氧化还原中心的分子的研究引起了材料科学领域的广泛研究兴趣。此外，这种具有两个以上氧化还原活性金属中心的分子对于通过这些多金属体系衍生的混合价态进行多电子转移过程的研究来说是一个极具吸引力的目标。另一方面，对通过使用包含第 16 族元素的 5π-和 7π-电子框架设计新型氧化还原活性有机中心的兴趣促使我们探索包含硫和/或硒原子的新型 5 元杂环的合成。因此，我们设计了2,3-二取代苯并[b]噻吩和1,3-二取代苯并[c]硫族酚作为阴极和阳极多重氧化还原活性有机-有机金属杂化分子。分别以苯并[b]噻吩或邻苯二甲酰二氯为原料，系统、选择性地合成了2,3-二取代苯并[b]噻吩、1,3-二取代苯并[c]噻吩和1,3-二取代苯并[c]硒吩。通过物理和光谱手段以及X射线晶体学分析进行分子表征。含有芳基片段的硫属酚衍生物的循环伏安图显示出源自异常稳定的5π硫属酚自由基阳离子和7π硫属酚自由基阴离子的明确的可逆阳极和阴极步骤。含有二茂铁基片段的新型硫族酚衍生物的循环伏安图显示出源自异常稳定的7π硫族酚自由基阴离子的明确的可逆阴极步骤和源自通过噻吩杂环彼此分隔的二茂铁阳离子的两个不同的可逆阳极步骤。通过ESR光谱法测量了几种新型7π硫族酚自由基阴离子的自由基特性。较少的

项目成果

Design of Reversible One-electron redox Systems Using Five-membered Heterocycles Containing Sulfur, Selenium, and Tellurium

使用含硫、硒和碲的五元杂环设计可逆单电子氧化还原系统

• 发表时间: 2004
• 期刊: J.Synthetic Organic Chemistry, Japan 62(No.2)
• 作者: S.Kobayashi;T.Nishikawa;T.Takenobu;S.Mori;T.Shimoda;T.Mitani;H.Shimotani;N.Yoshimoto;S.Ogawa;Y.Iwasa;S.Ogawa
• 通讯作者: S.Ogawa

半導体素子の製造方法、半導体素子および半導体装置

半导体元件的制造方法、半导体元件以及半导体装置

• 发表时间: 2005

N.Nagahora, S.Ogawa, S.Yoshimura, Y.Kawai, R.Sato: "Design of Reversible Low Redox Potential Systems Using Five-membered Trichalcogenaheterocycles Containing Heavy Chalcogens ; Sulfur, Selenium, and Tellurium"Bull.Chem.Soc.Jpn.. 76・5. 1043-1054 (2003)

N.Nagahora、S.Okawa、S.Yoshimura、Y.Kawai、R.Sato：“使用含有重硫属元素、硫、硒和碲的五元三硫族杂环设计可逆低氧化还原电位系统”Bull.Chem.Soc。日本.. 76・5. 1043-1054 (2003)

Efficient Synthesis, Structure, and Redox Reactions of 1,4,6,9‐Tetraisopropylchalcogenanthrenes.

1,4,6,9-四异丙基硫属蒽的高效合成、结构和氧化还原反应。

• DOI: 10.1002/chin.200630036
• 发表时间: 2006
• 期刊: ChemInform
• 作者: Tatsuya Yamamoto;S. Ogawa;M. Sugawara;Y. Kawai;R. Sato
• 通讯作者: R. Sato

Design of Reversible Organic-organometallic Multi-redox Systems Using Thianthrene Having Ferrocene Fragments

使用具有二茂铁片段的噻蒽的可逆有机-有机金属多重氧化还原体系的设计

• 发表时间: 2006
• 期刊: Tetrahedron Lett. 47(No.15)
• 作者: S.Ogawa;H.Muraoka;R.Sato
• 通讯作者: R.Sato