A time-resolved spectroscopy and density functional theory study of the solvent dependent photochemistry of fenofibric acid

Abstract

The solvent dependent photochemistry of fenofibric acid (FA) was studied by femtosecond transient absorption and nanosecond time-resolved resonance Raman experiments and density functional theory calculations. In acetonitrile-rich solution, a typical nπ* triplet state FA (³FA) is formed through a highly efficient intersystem crossing and then the ³FA species undergoes some reaction with water to generate a ketyl radical intermediate at low water concentrations. In contrast, nπ* ³FA changes from a reaction with water to generate a ketyl radical intermediate at lower water concentrations to a decarboxylation reaction with the assistance of water molecules to produce a biradical intermediate at higher water concentrations in water-rich solutions. The decarboxylation reaction leads to the formation of the FA carbanion in 50% phosphate buffer solution and the FA carbanion is observed on the picosecond to nanosecond time scale and the cleavage of the FA carbanion gives rise to the enolate 3⁻ anion at later nanosecond delay times. As regards fenofibrate (FB), it only exhibits a benzophenone-like photochemistry, which consists of some reaction with water to generate a ketyl radical intermediate, being observed in the different aqueous solutions.