Controlling the microadsorption structure of porphyrin dye assembly on clay surfaces using the "size-matching rule"...

The microadsorption structure of two kinds of porphyrin molecules on an anionic clay surface was investigated by photochemical energy transfer reaction. Three procedures were examined for the preparation of the clay/porphyrin complexes: (i) coadsorption (CA) method, (ii) sequential adsorption (SA) method, and (iii) independent adsorption (IA) method as described in the text. Efficient and moderate energy transfer reactions were observed in the CA and SA complexes, respectively. On the contrary, the energy transfer did not occur in the IA complex. These results indicate that the microadsorption structure of the two kinds of porphyrin on the clay mineral surface resulting from the sample preparation methods, affects the energy transfer efficiency. As a result, it was revealed that (i) the adsorbed porphyrins can move on the clay mineral surface but cannot move from one clay surface to another clay sheet, and (ii) the integration structure of two kinds of porphyrin is more stable than the segregation structure in the present system. This unusual structure originated from an extremely strong electrostatic interaction between the porphyrin and the clay mineral as a result of a "size-matching rule". These unique strongly fixed dye assemblies on the clay mineral surface, in which the aggregation and segregation of dyes are suppressed, is very promising and attractive for constructing efficient photochemical reaction systems.