Investigation of reactivity of organic radical cations in solution and at interface.

研究溶液和界面中有机自由基阳离子的反应性。

• 批准号: 14050008
• 负责人: IKEDA Hiroshi
• 金额: $ 17.73万
• 依托单位: Osaka Prefecture University (2006)Tohoku University (2002-2005)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14050008/
• 关键词: Photochemistry; Zeolite; Electron Transfer Reaction; Reaction Mechanism; Radical Cation; Biradical; Thermoluminescence; OLED; 光触媒; 光増感剤; 酸化チタン; Photochemistry; Zeolite; Electron Transfer Reaction; Reaction Mechanism; Radical Cation; Biradical; Thermoluminescence; OLED; 光触媒; 光増感剤; 酸化チタン

1. Investigation of Electronic Structures and Molecular Structures of Radical Cations Generated in Photoinduced Electron-Transfer.The electronic structures and molecular structures of radical cations generated in photoinduced electron-transfer (PET) was investigated by using organic and physical chemical experiments and theoretical calculations.As a result, we discovered a novel oxatetramethyleneethane radical cation, a distonic radical cation with or without orbital interaction, and nonclassical radical cation. In addition, we studied the observation of the excited biradical and its orbital interaction by using thennoluminescence. We found out that thennoluminescence is an effective tool of the observation of the transient intermediate that was rarely observed by absorption spectroscopy.2. A new organic functionalization of the zeolite surface oriented toward a photofunctionalized interface.We found that an HZSM-5-induced electron-transfer reaction of methylenecyclopropane derivative … More resulted in the formation of a persistent radical cation stabilized in an HZSM-5.3. Investigation of the mechanism of thermoluminescence of the open-shell species and development of organic light-emitting diodes (OLED).(I) Investigation of the mechanism of thermoluminescence of the open-shell species. The mechanism of the thenmoluminescence of methylenecyclopropane was studied. As a result, it was found that the thermoluminescence was originated from the excited state of trimethylenemethane biradical that is formed by back electron transfer from the substrate radical anion to the corresponding radical cation.(2) Development of Organic light-emitting Diodes (OLED). Next, a new concept of organic radical light-emitting diodes (ORLED), a new OLED using an electronically excited triplet trimethylenemethane biradical, is proposed. The mechanistic features of ORLED have the potential of overcoming significant problems (e. g. difficulty obtaining long wavelength emission, low quantum efficiency, and low device durability) associated with typical OLED that use organic closed-shell hydrocarbons. In fact, we manufactured a bilayer OLED using a methylenecyclopropane compound as a dopant and observed a electroluminescence from the corresponding excited biradical. Less

1。研究在光诱导的电子转移中产生的自由基阳离子的电子结构和分子结构。在光诱导的电子转移（PET）中产生的电子结构和分子结构通过有机和物理化学实验和理论进行了分裂，我们发现了一种新颖的氧化氧化物，我们通过有机和物理化学实验和理论进行了分裂，我们发现了一个或理论。轨道相互作用和非经典阳离子。此外，我们通过使用含量发光研究了激发的Biradical及其轨道相互作用的观察。我们发现当时的发光是观察瞬态中间体的有效工具，这很少通过抽象光谱观察到。2。我们发现，将沸石表面朝向光功能化的界面的新有机化。我们发现，甲基丙烷丙烷衍生物的HZSM-5诱导的电子转移反应……更多地导致形成在HZSM-5.3中持续稳定的自由基阳离子。研究开放壳物种的热发光机理以及有机发光二极管（OLED）的发展。随后的甲基苯丙烷的粉状发光的机理是研究的。结果，发现热发光最初起源于三甲基甲烷Biradical的激发状态，该状态是由从底物自由基阴离子到相应自由基阳离子的背部传递形成的。接下来，提出了一个新的有机自由基发光二极管（Orled）的概念，这是一种使用电子激发的三甲基甲基甲烷Biradical的新OLED。 Orled的机械特征具有克服重大问题（例如，难以获得长波长发射，低量子效率和低设备耐用性）与使用有机封闭壳碳氢化合物相关的典型OLED。实际上，我们使用甲基丙烷丙烷化合物作为掺杂剂制造了双层OLED，并观察到来自相应的令人兴奋的Biradical的电致发光。较少的