Differential photoactivity of aqueous [C60] and [C70] fullerene aggregates

Many past studies have focused on the aqueous photochemical properties of colloidal suspensions of C60 and various [C60] fullerene derivatives, yet few have investigated the photochemistry of other larger cage fullerene species (e.g., C70, C74, C84, etc.) in water. This is a critical knowledge gap because these larger fullerenes may exhibit different properties compared to C60, including increased visible light absorption, altered energy level structures, and variable cage geometries, which may greatly affect aggregate properties and resulting aqueous photoactivity. Herein, we take the first steps toward a detailed investigation of the aqueous photochemistry of larger cage fullerene species, by focusing on [C70] fullerene. We find that aqueous suspensions of C60 and C70, nC60 and nC70, respectively, exhibit many similar physicochemical properties, yet nC70 appears to be significantly more photoactive than nC60. Studies are conducted to elucidate the mechanism behind nC70's superior (1)O2 generation, including the measurement of (1)O2 production as a function of incident excitation wavelength, analysis of X-ray diffraction data to determine crystal packing arrangements, and the excited state dynamics of aggregate fullerene species via transient absorption spectroscopy.