Structural, Photophysical, and Photochemical Characterization of 9-Anthracenecarboxylate−Hydrotalcite Nanocomposites: Evidence of a Reversible Light-Driven Reaction

Abstract

ZnAl hydrotalcites containing increasing amounts of 9-anthracenecarboxylate anion (9AC) have been obtained via an anion-exchange procedure. In particular, intercalated and/or surface-exchanged samples were prepared to study the effect of the chromophore packing on their photophysical and photochemical behavior. Surface-exchanged samples were obtained by equilibrating the carbonate form of the ZnAl hydrotalcite with dilute solutions of 9AC. The nitrate form of the ZnAl hydrotalcite was instead chosen for the preparation of intercalation compounds. The maximum loading of 9AC was found to be 44% of the anion-exchange capacity. The obtained nanostructured materials were characterized by chemical and thermal analysis and X-ray powder diffractometry and studied for their photophysical and photochemical properties. The absorption and emission spectra of the materials revealed the formation of 9AC aggregates. The time-resolved fluorescence properties of the hybrid materials were investigated in bulk and under space-resolved conditions. The fluorescence decays appeared to be quite complex and were affected by the microenvironment and the experimental conditions. Generally, a shortening of the main fluorescence decay component was observed with increasing matrix loading, thus suggesting the occurrence of nonradiative processes in competition with fluorescence at high chromophore concentrations. Indeed, the occurrence of an electron-transfer process to water molecules, which led to the formation of 9AC radical, was observed spectrophotometrically in the sample with high 9AC loading. The electron-transfer process was completely reversible under air-equilibrated conditions.