Elucidating the photoprotective properties of natural UV screening agents: ZEKE-PFI spectroscopy of methyl sinapate

Abstract

As a prominent derivative of a natural sunscreen, methyl sinapate is an ideal candidate to provide fundamental insight into strategies on how to come to a rational design of artificial sunscreen filters with improved photoprotective properties. Here, static and time-resolved Zero Kinetic Energy-Pulsed Field Ionization (ZEKE-PFI) photoelectron spectroscopy has been used to study the spectroscopy and decay pathways of its electronically excited states. We find that different conformers are subject to distinct structural changes upon electronic excitation, and trace the structural changes that occur upon excitation back to the character of the LUMO. Ionization efficiency spectra in combination with pump-probe ZEKE-PFI spectra are consistent with the conclusion that the long-lived electronically excited state observed in the decay of the lowest excited singlet state is the lowest excited triplet state. Concurrently with providing information on the electronically excited states, the studies allow for a detailed characterization of the spectroscopic properties of the ground state of the radical ion, which is important in the context of the use of cinnamates in nature as antioxidants. Our studies determine the adiabatic ionization energies of the syn/cis, anti/cis and anti/trans conformers as 60 291.1 ± 0.5, 60 366.9 ± 0.5 and 60 503.9 ± 1.0 cm-1, respectively, and provide accurate vibrational fequencies of low-frequency modes of the molecular ion in its electronic ground state. Finally, the studies emphasize the important role of vibrational and electronic autoionization processes that start to dominate the ionization dynamics in non-rigid molecules of the present size.