Intramolecular Energy Transfer in Covalently Linked Polypyridine Ruthenium(II)/Osmium(II) Binuclear Complexes. Ru(II)(bpy)2Mebpy-(CH2)n-MebpyOs(II)(bpy)2 (n=2, 3, 5, and 7).

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概要

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• A novel series of polymethylene-linked heterobinuclear complexes of polypyridine ruthenium(II)/osmium(II) complex Ru(II)(bpy)<SUB>2</SUB>Mebpy–(CH<SUB>2</SUB>)<I><SUB>n</SUB></I>–MebpyOs(II)(bpy)<SUB>2</SUB>(bpy=2,2′-bipyridine and <I>n</I>=2, 3, 5, and 7), <B>1</B>, was prepared. The photophysical behavior was examined in various solvents. The emission spectra of <B>1</B> (excitation wavelength: 455nm) showed a nearly complete quenching of Ru<SUP>II</SUP>→π<SUP>*</SUP>(bpy) metal-to-ligand charge transfer (MLCT) emission and the enhancement of Os<SUP>II</SUP>→π<SUP>*</SUP>(bpy) MLCT emission. The luminescence lifetime measurements by a time-correlated single photon-counting method provided evidence that intramolecular energy transfer is a significant pathway for the observed emission quenching. The rate constants of the intramolecular energy transfer in ethanol are 5.3×10<SUP>8</SUP>, 3.3×10<SUP>8</SUP>, 1.3×10<SUP>8</SUP>, and 1.0×10<SUP>8</SUP>s<SUP>−1</SUP> for <B>1</B>(<I>n</I>=2, 3, 5, and 7), respectively. They were found to be proportional to the inverse sixth power on the center-to-center distance of the two complexes. The mechanism is discussed in terms of the Förster (a dipole-dipole interaction) mechanism.

• 公益社団法人 日本化学会の論文

著者

• Kinoshita Shuichi

  Department Of Electrical Engineering National Defense Academy

• Kushida Takashi

  Department Of Physics Faculty Of Science Osaka University

• Kamachi Mikiharu

  Department Of Macromolecular Science Faculty Of Science Osaka University

• KUSHIDA Takashi

  Department of Physics, Faculty of Science, Osaka University

• Nozakura Shun-ichi

  Department of Macromolecular Science, Faculty of Science, Osaka University

• Furue Masaoki

  Department of Macromolecular Science, Faculty of Science, Osaka University

• Yoshidzumi Toshiyuki

  Department of Macromolecular Science, Faculty of Science, Osaka University

• Kamachi Mikiharu

  Department of Macromolecular Chemistry, Faculty of Science, Osaka University

• Kinoshita Shuichi

  Department of Chemistry, Faculty of Science, University of Tokyo

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