A new insight into the photochemistry of avobenzone in gas phase and acetonitrile from ab initio calculations

Abstract

Avobenzone (4-tert-butyl-4′-methoxydibenzoylmethane, AB) is one of the most widely used filters in sunscreens for skin photoprotection in the UVA band. The photochemistry of AB includes keto–enol tautomerization, cis–trans isomerization, rotation about the single bond and α bond cleavages of carbonyl groups. In this contribution we study chelated and non-chelated enol, rotamers Z and E, and keto tautomers of AB in the ground and excited states in gas phase and acetonitrile by means of a coupled cluster method. Our findings suggest that torsion around the double C2–C3 bond of photoexcited chelated enol leads to internal conversion to the ground state and formation of rotamer E. In addition, opening of the chelated hydrogen ring by torsion of the hydroxyl group creates non-chelated enol. The possible mechanisms of rotamer Z formation are discussed. The solvent dependent photolability is related to the relative order of the lowest triplet ππ* and nπ* states of the keto tautomer.