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

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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