Ultrafast excited-state dynamics of 4-hydroxychalcone: role of intramolecular charge transfer and photoacidity

Abstract

Diarylketones such as benzophenones, oxybenzones, chalcones and their derivatives exhibit promising applications as UV filters/sunscreen agents due to their effective absorption in the UV region and dissipation through non-radiative pathways. However, elucidation of the underlying photoreactive mechanism is non-trivial due to the ultrafast lifetimes of transient species, involvement of non-adiabatic curve crossings among the potential surfaces, etc. In this context, we investigate the excited-state photoreaction dynamics of 4-hydroxychalcone (4-HC) under various environments through femtosecond-transient absorption (fs-TA), nanosecond-transient absorption (ns-TA), and femtosecond-fluorescence upconversion (fs-FL) measurements. Steady-state fluorescence measurements of 4-HC in the presence of 1-methylimidazole (MI)/tert-butylamine (TBA) exhibit dual band emission. The fs-TA measurements of 4-HC in the presence of MI/TBA exhibit distinct spectral and associated lifetimes as compared to 4-HC alone indicating a significant interaction of the hydroxyl proton with bases and influencing the reaction dynamics. The 4-HC:MI/TBA adduct undergoes excited-state intermolecular proton transfer within a time scale of ∼500 fs and subsequently relaxes back to the ground state through a long-lived triplet state. The experimental observations of excited-state reaction dynamics of 4-HC in the presence of MI/TBA bases have been well corroborated with the computational analysis.