Spectral study on the molecular orientation of a tetracationic porphyrin dye on the surface of layered silicates

Alexander Čeklovský 1 , Juraj Bujdák 1 , Adriana Czímerová 1 , and Nobuo Iyi 2
  • 1 Department of Hydrosilicates, Institute of Inorganic Chemistry, Slovak Academy of Sciences, 842 36, Bratislava, Slovakia
  • 2 National Institute for Materials Science, Namiki 1-1, Tsukuba, Ibaraki, 305-0044, Japan


Tetracationic porphyrin dyes TMPyP and ZnPyP were intercalated into hydrophobized layered silicate films of three smectites. The smectites represented the layered silicate specimens of high (Fluorohectorite, Corning; FHT), medium (Kunipia F montmorillonite; KF) and low layer charge (Laponite, Laporte; LAP). The molecular orientations of the dye cations were studied by means of linearly-polarized ultraviolet-visible (UV-VIS) spectroscopy. The spectral analysis and consequent calculations of tilting angles of the transition moments at the wavelengths of Soret band transitions were in the range of 25°-35°. The determined angles indicated molecular orientation of the dye cations being almost parallel to the surface of the silicates. Slightly higher values (above 35°), determined for a FHT film, indicated either a slightly tilted orientation of the dye cations or the change of molecular comformation after the intercalation of the dye.

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