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

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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