Acceleration of photochromism and negative photochromism by the interactions with mesoporous silicas

The adsorption of merocyanine dye onto mesoporous silicas with varied pore sizes (5.5, 9.4 and 2.2 nm) from the toluene solution of 1,3,3-trimethylindolino-6'-nitrobenzopyrylospiran under UV irradiation was investigated quantitatively. The photoinduced adsorption of merocyanine onto SBA-15 with the pore diameter of 9.4 nm followed the pseudo-second order kinetics and the rate constant was larger than that observed for MCM-41 (pore size of 2.2 nm) owing to the efficient diffusion of merocyanine. The maximum adsorbed amounts of the merocyanine dye was 152 mg g-1 of SBA-15, which corresponded to the sufficiently high concentration of merocyanine in the pores (0.376 mol L-1 of pore). The resulting red-colored hybrids (SBA-15 containing merocyanine) showed decoloration in the solid-state by visible light irradiation (negative photochromism). The conversion was high (about 80% at the photostationary state) under visible light irradiation at room temperature using a solar simulator (100 W). The red color was re-generated by storing the photochemically formed colorless samples in the dark at room temperature. The half-lives of the thermal coloration process were 2.6, 1.9 and 1.3 h for the MCM-41, SBA-15s with the BJH pore sizes of 5.5 and 9.4 nm, respectively. Since the coloration was affected by the diffusion of the molecules in the pores, larger pores provided the efficient molecular diffusion, leading to faster reactions.