Photoexcited triplet states of new UV absorbers, cinnamic acid 2-methylphenyl esters

Abstract

Phosphorescence spectra of nonphosphorescent or very weakly phosphorescent new UV absorbers, 2-methylphenyl cinnamate (MePC), 2-methylphenyl 4-methoxycinnamate (MePMC) and 2-methylphenyl 4-ethoxycinnamate (MePEC) have been observed by using external heavy atom effects of ethyl iodide in ethanol at 77 K. The lowest excited triplet (T1) energies of these new UV absorbers are lower than those of a widely used UV-A absorber, 4-tert-butyl-4′-methoxydibenzoylmethane (BM-DBM), in both keto and enol forms. The intermolecular triplet-triplet energy transfer from photolabile BM-DBM to MePMC was observed by measuring the time-resolved phosphorescence spectra. Electron paramagnetic resonance spectra have been observed for the T1 states of these new UV absorbers in ethanol at 77 K by using benzophenone as a triplet sensitizer. The observed T1 lifetimes, zero-field splitting (ZFS) parameters and molecular orbital calculations of the ZFS parameters suggest that T1 states of these new UV absorbers posses mainly 3ππ* character. The deactivation processes of the lowest excited singlet (S1) states are predominantly fluorescence and internal conversion to the ground (G) states in MePMC and MePEC, while the main deactivation process of the S1 state of MePC is internal conversion to the G state. The molar absorption coefficients of MePMC and MePEC in the UV-A and UV-B regions are larger than that of most widely used UV-B absorber, octyl methoxycinnamate. © 2011 The Royal Society of Chemistry and Owner Societies.