OPTICAL INVESTIGATIONS OF THE CHEMICAL MICROENVIRONMENT WITHIN THE LAYERED SOLID ZIRCONIUM-PHOSPHATE SULFOPHENYLPHOSPHONATE
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Yang and Clearfield have recently described a sulfonated derivative of the layered solid -zirconium phosphate. This new layered solid ion exchanger (zirconium phosphate sulfophenylphosphonate, ZrPS) incorporates Ru(bpy)32+ (bpy = 2,2-bipyridine) via ion exchange. This optical probe ion was used to investigate the chemical microenvironment within ZrPS. Ru(bpy)32+ shows pronounced spectral shifts in both its absorption and emission spectra (relative to water) when incorporated into ZrPS. Similar spectral shifts have been observed for Ru(bpy)32+ in other chemical microenvironments (e.g., micelles, clays, vesicles). These shifts have been explained by invoking microenvironment-induced changes in the chemical, structural, and electrochemical characteristics of the complex itself. We show here that none of these explanations applies to ZrPS. Rather, the observed spectral shifts when Ru(bpy)32+ is incorporated into ZrPS result from interactions of the complex with the phenyl rings of the host and the bipyridyl rings of neighboring complexes. 1988 American Chemical Society.