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

Central European Journal of Physics - Tập 5 - Trang 236-243 - 2007
Alexander Čeklovský1, Juraj Bujdák1, Adriana Czímerová1, Nobuo Iyi2
1Department of Hydrosilicates, Institute of Inorganic Chemistry, Slovak Academy of Sciences, Bratislava, Slovakia
2National Institute for Materials Science, Namiki 1-1, Tsukuba, Ibaraki, Japan

Tóm tắt

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.

Tài liệu tham khảo

J. Bujdák and N. Iyi: “Molecular orientation of rhodamine dyes on surfaces of layered silicates”, J. Phys. Chem. B, Vol. 109, (2005), pp. 4608–4615. J. Bujdák, N. Iyi, Y. Kaneko, A. Czímerová and R. Sasai: “Molecular arrangement of Rhodamine 6G cations in the films of layered silicates: the effect of the layer charge”, Phys. Chem. Chem. Phys., Vol. 5, (2003), pp. 4680–4685. V.R.L. Constantino, C.A.S. Barbosa, M.A. Bizeto and P.M. Dias: “Intercalation comounds involving inorganic layered structures”, An. Acad. Bras. Cienc., Vol. 72, (2000), pp. 45–49. A. Czímerová, J. Bujdák and A. Gáplovský: “The aggregation of thionine and methylene blue dye in smectite dispersion”, Colloid. Surface. A: Physicochem. Eng. Aspects, Vol. 243, (2004), pp. 89–96. G. Chen, N. Iyi, R. Sasai, T. Fujita and K. Kitamura: “Intercalation of rhodamine 6G and oxazine 4 into oriented clay films and their alignment”, J. Mater. Res., Vol. 17, (2002), pp. 1035–1040. Z. Chernia and D. Gill: “Flattening of TMPyP adsorbed on laponite. Evidence in observed and calculated UV-VIS spectra”, Langmuir, Vol. 15, (1999), pp. 1625–1633. J. Dargiewicz, M. Makarska and S. Radzki: “Spectroscopic characterisation of watersoluble cationic porphyrins in sol-gel silica matrices and coatings”, Colloid. Surface. A: Physicochemical and Engineering Aspects, Vol. 208, (2002), pp. 159–165. P.M. Dias, D.L.A. de Faria and V.R.L. Constantino: “Spectroscopic studies on the interaction of tetramethylpyridylporphyrins and cationic clays”, J. Incl. Phen. and Macro. Chem., Vol. 38, (2000), pp. 251–266. M. Eguchi, S. Takagi, H. Tachibana and H. Inoue: “The size matching rule in di-,tri-, and tetra-cationic charged porphyrin/synthetic clay complexes: effect of the inter-charge distance and the number of charged sites”, J. Phys. Chem. Solids, Vol. 65, (2004), pp. 403–407. M. Makarska, S. Radzki and J. Legendziewicz: “Spectroscopic characterisation of the water-soluble cationic porphyrins and their complexes with Cu(II) in various solvents”, J. Alloy. Compd., Vol. 341, (2002), pp. 233–238. M. Ogawa and K. Kuroda: “Photofunctions of intercalation compounds”, Chem. Rev., Vol. 95, (1995), pp. 399–438. R. Sasai, N. Iyi, T. Fujita, F. López Arbeloa, V. Martínez Martínez, K. Takagi and H. Itoh: “Luminescence properties of rhodamine 6G intercalated in surfactant/clay hybrid thin solid films”, Langmuir, Vol. 20, (2004), pp. 4715–4719. S. Takagi, T. Shimada, T. Yui and H. Inoue: “High density adsorption of porphyrins onto clay layer without aggregation: characterisation of smectite-cationic porphyrin complex”, Chem. Lett., (2001), pp. 128–129. S. Takagi, T. Shimada, M. Eguchi, T. Yui, H. Yoshida, D.A. Tryk and H. Inoue: “High-density adsorption of cationic porphyrins on cla layer surfaces without aggregation: the size-matching effect”, Langmuir, Vol. 18, (2002), pp. 2265–2272. T. Yui and K. Takagi: “Photochemistry of laminate type organic/inorganic hybrid compounds”, J. Soc. Photographic Sci. Tech. Jpn., Vol. 66, (2003), pp. 326–340.