Influence of the Solvent Environment on the Ultrafast Relaxation Pathways of a Sunscreen Molecule Diethylamino Hydroxybenzoyl Hexyl Benzoate

Min Hsien Kao, Ravi Kumar Venkatraman, Mahima Sneha, Matthew Wilton, Andrew J. Orr-Ewing*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

20 Scopus citations

Abstract

The excited-state dynamics of photoexcited diethylamino hydroxybenzoyl hexyl benzoate (DHHB), a UVA absorber widely used in sunscreen formulations, are studied with transient electronic and vibrational absorption spectroscopy methods in four different solvents. In the polar solvents methanol, dimethyl sulfoxide (DMSO), and acetonitrile, strong stimulated emission (SE) is observed at early time delays after photoexcitation at a near-UV wavelength of λex = 360 nm, and decays with time constants of 420 fs in methanol and 770 fs in DMSO. The majority (μ95%) of photoexcited DHHB returns to the ground state with time constants of 15 ps in methanol and 25 ps in DMSO. In the nonpolar solvent cyclohexane, ∼98% of DHHB photoexcited at λex = 345 nm relaxes to the ground state with a ∼10 ps time constant, and the SE is weak. DHHB preferentially adopts an enol form in its ground S0 state, but excited state absorption (ESA) bands seen in TEAS are assigned to both the S1-keto and S1-enol forms, indicating a role for ultrafast intramolecular excited state hydrogen transfer (ESHT). This ESHT is inhibited by polar solvents. The two S1 tautomers decay with similar time scales to the observed recovery of ground state population. For molecules that avoid ESHT, torsion around a central C-C bond minimizes the S1-enol energy, quenches the SE, and is proposed to lead to a conical intersection with the S0 state that mediates the ground state recovery. A competing trans-enol isomeric photoproduct is observed as a minor competitor to parent recovery in polar solvents. Evidence is presented for triplet (T1) enol production in polar solvents, and for T1 quenching by octocrylene, a common UVB absorber sunscreen additive. The T1 keto form is observed in cyclohexane solution.

Original languageEnglish
Pages (from-to)636-645
Number of pages10
JournalJournal of Physical Chemistry A
Volume125
Issue number2
DOIs
StatePublished - 21 Jan 2021
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2021 American Chemical Society.

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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