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

1. 光诱导电子转移中自由基阳离子的电子结构和分子结构研究。采用有机化学实验、物理化学实验和理论计算研究了光致电子转移（PET）中自由基阳离子的电子结构和分子结构。结果，我们发现了一种新的氧四甲基乙烷自由基阳离子，一种具有或不具有轨道相互作用的双离子自由基阳离子，以及一种非经典自由基阳离子。此外，我们还研究了用微致发光观察激发态双基及其轨道相互作用。我们发现，微致发光是一种有效的观察瞬态中间体的工具，这是吸收光谱很难观察到的。一种面向光功能化界面的新型有机功能化沸石表面。我们发现hzsm -5诱导的亚甲基环丙烷衍生物的电子转移反应导致了在HZSM-5.3中稳定的持久性自由基阳离子的形成。开壳材料热致发光机理的研究及有机发光二极管（OLED）的研制。(1)开壳物种热释光机理的研究。研究了亚甲基环丙烷的热释光机理。结果发现，热致发光源于三甲基乙烷双自由基的激发态，该激发态是由底物自由基阴离子向相应的自由基阳离子的反向电子转移而形成的。(2)有机发光二极管（OLED）的发展。其次，提出了一种新的有机自由基发光二极管（ORLED）的概念，一种使用电子激发三重态三甲基乙烷双自由基的新型OLED。ORLED的机械特性有可能克服与使用有机闭壳烃的典型OLED相关的重大问题（例如难以获得长波发射，低量子效率和低器件耐用性）。事实上，我们使用亚甲基环丙烷化合物作为掺杂剂制造了双层OLED，并观察到相应的激发双基的电致发光。少

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