Control of Structure and Photoproperties on Cationic Tetraphenylporphyrinatoantimony(V)/Synthetic Clay Composites

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Novel metalloporphyrin-clay composites were prepared from a synthetic clay (Sumecton SA ; SSA) and cationic tetrapheylporphyrinatoantimony(V) bromide (SbTPP) having various axial ligand. Both the crystal structure for SbTPP-SSA composites and the adsorption behaviors of SbTPP into SSA sheets were investigated regarding the relation to the structure of an axial ligand at SbTPP by measuring XRD, IR, UV-vis, and fluorescence spectroscopy. It,was clear that an axial ligand structure can control not only the formation of the crystal structure, but also the adsorption behaviors with aggregation or non-aggregation onto SSA sheets.SbTPP dyes-adsorbed SSA nano-clay sheets films were prepared on a glass plate modified with ammonium cation (MAS-glass). The dispersibility of SbTPP-adsorbed SSA sheets strongly depended on the surface state of a glass plate. The fluorescence images emitting from the films were analyzed by a confocal laser scanning fluorescence microscope, revealing that SbTPP dyes are adsorbed onto nano-SSA sheets without their aggregation. The photochemical behavior between SbTPP and pyranine co-adsorbed onto SSA sheets was also investigated. The fluorescence of pyranine was extremely quenched with an increase of an adsorption amount of SbTPP, suggesting that the photochemical electron transfer from excited ptranine to SbTPP should occur on nano-SSA sheets. The dye-clay composites in which dye molecules adsorb without aggregation could be promising for constructing intermolecular photochemical reaction onto nano-clay sheets system.