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

以合成粘土（Sumecton SA； SSA）和具有不同轴向配体的阳离子四烷基卟啉锑(V)溴化（SbTPP）为原料，制备了新型金属卟啉-粘土复合材料。通过XRD、IR、UV-vis和荧光光谱分析，研究了SbTPP-SSA复合材料的晶体结构和SbTPP在SSA片上的吸附行为，以及SbTPP与轴向配体结构的关系。可见，轴向配体结构不仅可以控制晶体结构的形成，还可以控制SSA片上聚集或非聚集的吸附行为。在铵离子改性玻璃板上制备了SbTPP染料吸附的SSA纳米粘土片膜。sbtpp吸附的SSA片材的分散性很大程度上取决于玻璃板的表面状态。用共聚焦激光扫描荧光显微镜分析了膜上的荧光图像，发现SbTPP染料被吸附在纳米ssa片上而没有聚集。研究了SbTPP与吡啶在SSA片上共吸附的光化学行为。随着SbTPP吸附量的增加，pyranine的荧光被极度猝灭，这表明在纳米ssa片上发生了从受激的ptranine到SbTPP的光化学电子转移。染料分子吸附而不聚集的染料-粘土复合材料有望在纳米粘土片上构建分子间光化学反应。

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.