The Mechanism of the Porphyrin Spectral Shift on Inorganic Nanosheets: The Molecular Flattening Induced by the Strong Host–Guest Interaction due to the “Size-Matching Rule”

  • Yohei Ishida
    Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan University, Minami-ohsawa 1-1, Hachiohji, Tokyo 192-0397 Japan
  • Dai Masui
    Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan University, Minami-ohsawa 1-1, Hachiohji, Tokyo 192-0397 Japan
  • Tetsuya Shimada
    Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan University, Minami-ohsawa 1-1, Hachiohji, Tokyo 192-0397 Japan
  • Hiroshi Tachibana
    Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan University, Minami-ohsawa 1-1, Hachiohji, Tokyo 192-0397 Japan
  • Haruo Inoue
    Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan University, Minami-ohsawa 1-1, Hachiohji, Tokyo 192-0397 Japan
  • Shinsuke Takagi
    Department of Applied Chemistry, Graduate Course of Urban Environmental Sciences, Tokyo Metropolitan University, Minami-ohsawa 1-1, Hachiohji, Tokyo 192-0397 Japan

書誌事項

公開日
2012-03-28
資源種別
journal article
DOI
  • 10.1021/jp300842f
公開者
American Chemical Society (ACS)

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説明

The mechanism inducing the unique absorption spectral shifts of porphyrin molecules upon adsorption on the clay surface was experimentally confirmed to be the flattening of the meso substituent with respect to the plane of the porphyrin ring. We investigated the spectral shift systematically by using seven types of porphyrin derivatives, differing in their center metal, meso substituent, and number of cationic sites. The aggregation, which usually induces the spectral shift, is suppressed in our clay/porphyrin systems. The adsorption strengths of porphyrin molecules on the clay surface were estimated as the relative adsorption equilibrium constants Krel. The seven types of porphyrins studied had different values of Krel, which can be explained by the steric effect and the Coulomb interaction due to the differences in the molecular structure. The obtained Krel values have interesting information of the photochemical property of the clay/porphyrin complexes. The absorption spectral shifts of the porphyrin S...

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