Physicochemical properties of polyacrylates containing tetraphenyl-prophinatocobalt(II) and chloro(tetraphenyl-porphinato)iron(III) as side chains.
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概要
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Polyacrylates containing tetraphenylporphinatocobalt(II) (TPP-Co(II)) and chloro(tetraphenylporphinato)iron(III) (TPP-Fe(III)Cl) as side chains were prepared. Their physicochemical properties were investigated by UV-visible spectroscopy, ESR spectroscopy, and magnetic susceptibility (χ<SUB>M</SUB>) measurement. In comparison of the visible spectra of polymers with those of the corresponding monomers, hypochromism of the Soret band and some of Q bands was observed in both polymers. In the measurements of ESR spectra, hyperfine splitting constants and anisotropic <I>g</I>-values of TPP-Co(II) or -Fe(III)Cl moieties bound to the polymers were somewhat different from those of TPP-Co(II) and -Fe(III)Cl, respectively. These differences in spectroscopic behavior suggest that there are some interactions between porphinatometal ion moieties in the polymers. The values of χ<SUB>M</SUB> for the polymers containing TPP-Co(II) were found to obey the Curie–Weiss law with θ=190 K, which was explained in terms not only of spin-orbit interaction of the Co(II) ion but also antiferromagnetic interaction among the Co(II) ions. The magnetic moment of the TPP-Co(II) moiety bound to the polymer is smaller than that of TPP-Co(II), indicating occurrence of an antiferromagnetic interaction between Co(II) ions in the polymer. The values of χ<SUB>M</SUB> for polymers containing TPP-Fe(III)Cl were found to obey the Curie–Weiss law with θ=20 K. This can be explained in terms of the presence of antiferromagnetically-interacting sites. From the experimental results, it is concluded that the antiferromagnetic interaction between TPP-metal ions bound to the polymer is larger than that of the corresponding TPP-metal ions. Molecular oxygen is adsorbed to polyAOTPP-Co(II) and 5-(4-propanoyloxyphenyl)-10,15,20-triphenylporphinatocobalt(II) (POTPP-Co(II)) below 180 K. Magnetic susceptibility measurement and ESR study show that molecular oxygen is bound to the Co(II) ion by chemisorption whose binding energy is 24 kJ M<SUP>−1</SUP>.
- 公益社団法人 日本化学会の論文
著者
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Mori Wasuke
Department Of Chemistry Faculty Of Science Kanagawa University
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Kishita Michihiko
Department Of Chemistry Faculty Of Science Kanagawa University
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Kamachi Mikiharu
Department of Macromolecular Chemistry, Faculty of Science, Osaka University
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Shibasaka Mahito
Department of Macromolecular Science, Faculty of Science, Osaka University
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Kajiwara Atushi
Department of Macromolecular Science, Faculty of Science, Osaka University
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