Picosecond laser spectroscopy of intramolecular heteroexcimer systems. Time-resolved fluorescence studies of p-(CH3)2NC6H4-(CH2)n-(9-anthryl),p-(CH3)2NC6H4-(CH2)n-(1-pyrenyl) systems and 9,9'-bianthryl.

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概要

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• In order to elucidate the details of elementary processes of photochemical charge transfer and heteroexcimer formation processes, and also in order to compare the obtained results with those of transient absorption spectral measurements, we have examined the following intramolecular heteroexcimer systems by means of ps time-resolved fluorescence measurements with a mode-locked Nd<SUP>3+</SUP>: YAG laser and a streak camera: <I>p</I>-(CH<SUB>3</SUB>)<SUB>2</SUB>–NC<SUB>6</SUB>H<SUB>4</SUB>–(CH<SUB>2</SUB>)<I><SUB>n</SUB></I>–(9-anthryl) (<I>n</I>=0, 1, 2, 3), <I>p</I>-(CH<SUB>3</SUB>)<SUB>2</SUB>NC<SUB>6</SUB>H<SUB>4</SUB>–(CH<SUB>2</SUB>)<I><SUB>n</SUB></I>-(1-pyrenyl) (<I>n</I>=1, 2, 3) and 9,9′-bianthryl. Effects of methylene chain length, solvent polarity and viscosity upon the intramolecular charge transfer processes have been clearly demonstrated. It is concluded that molecules with sandwich configuration in the ground state are not recognized in both <I>n</I>=3 compounds, and it takes a few ns for the heteroexcimer formation in hexane because of an extensive conformation change necessary to take sandwich configuration. Both conformation change and solvent reorientation are involved in the heteroexcimer formation processes in polar solvents, and heteroexcimer formation becomes faster with increase of solvent polarity and decrease of its viscosity. Moreover, two step conformation changes are observed in the case of the heteroexcimer formation of <I>n</I>=3 compounds in polar solvents, <I>i.e.</I> a heteroexcimer with loose structure is formed first, and then follows a structural change to the one of sandwich type. In acetonitrile, a strongly polar solvent, formation of heteroexcimer is very fast, occurring within the time-resolution of the picosecond apparatus.

• 公益社団法人 日本化学会の論文

著者

• SAKATA Yoshiteru

  Institute of Science and Industrial Research, Osaka University

• NAKASHIMA Nobuaki

  Institute of Environmental Toxicology

• Mataga Noboru

  Department Of Chemistry Faculty Of Engineering Science Osaka University

• YOSHIHARA Keitaro

  Institute for Molecular Science

• Okada Tadashi

  Department Of Chemistry Graduate School Of Engineering Science And Research Center For Materials Sci

• Migita Masahito

  Department of Chemistry, Faculty of Engineering Science, Osaka University

• Misumi Soichi

  Institute of Scientific and Industrial Research, Osaka University

• Nakashima Nobuaki

  Institute for Molecular Science

• Mataga Noboru

  Department of Chemistry, Faculty of Engineering Science, Osaka University

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