A UNIQUE "FLATTENING EFFECT" OF CLAY ON THE PHOTOCHEMICAL PROPERTIES OF METALLOPORPHYRINS(2010 TMC Special Paper)
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概要
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Clay-porphyrin complex formation and spectral behaviour of metalloporphyrins containing di-, tri- and tetravalent central metals with synthetic clay were examined. The spectral shift of porphyrin Soret band to higher wavelengths was observed upon the complex formation, where the clay sheets were either exfoliated or stacked in aqueous colloidal suspension. Moreover, the degree of the spectral shift decreased as the valence of porphyrin central metal increased. Since tri- and tetravalent metals have one and two axial ligands, respectively, their steric effect on porphyrin ring plane affected the extent of the "flattening" (i.e. co-planarization of porphyrin ring and peripheral aromatic rings) on the clay surface, thus influencing the spectral shift in porphyrin absorption spectra. These observations support the proposed hypothesis that "flattening" of porphyrin molecules on the clay surface induces the spectral shift of porphyrin Soret band. With this "flattening effect" of the clay surface, the λ_<max> value of Mg(II)TMPyP porphyrin reached up to 500nm in the stacked clay complex. These results indicate that the utilizing a combination of porphyrin with clay turned out to be unique to control the photochemical properties of porphyrins.
著者
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TAKAGI SHINSUKE
Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan
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KONNO SAKI
Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan
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ISHIDA YOHEI
Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan
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CEKLOVSKY ALEXANDER
Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan
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MASUI DAI
Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan
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SHIMADA TETSUYA
Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan
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TACHIBANA HIROSHI
Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan
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INOUE HARUO
Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan
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Masui Dai
Department Of Applied Chemistry Graduate Course Of Urban Environmental Sciences Tokyo Metropolitan U
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Konno Saki
Department Of Applied Chemistry Graduate Course Of Urban Environmental Sciences Tokyo Metropolitan U
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Inoue H
Department Of Applied Chemistry Graduate Course Of Urban Environmental Sciences Tokyo Metropolitan U
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Inoue Haruo
Department Of Applied Chemistry Graduate Course Of Engineering Tokyo Metropolitan University
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Ishida Yohei
Department Of Applied Chemistry Graduate Course Of Urban Environmental Sciences Tokyo Metropolitan U
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Inoue Haruo
Department Of Applied Chemistry Graduate School Of Engineering Tokyo Metropolitan University
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Inoue H
Crest Jst (japan Science And Technology)
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Takagi Shinsuke
Department Of Applied Chemistry Graduate Course Of Urban Environmental Sciences Tokyo Metropolitan U
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Takagi Shinsuke
Department Of Industrial Chemistry Faculty Of Technology Tokyo Metropolitan University
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Shimada Tetsuya
Department Of Applied Chemistry Graduate Course Of Urban Environmental Sciences Tokyo Metropolitan U
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Tachibana Hiroshi
Department Of Applied Chemistry Graduate Course Of Urban Environmental Sciences Tokyo Metropolitan U
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Ceklovsky Alexander
Department Of Applied Chemistry Graduate Course Of Urban Environmental Sciences Tokyo Metropolitan U
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Takagi S
Nagoya Inst. Technology Nagoya
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Shimada T
Department Of Applied Chemistry Shibaura Institute Of Technology
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