Towards a photophysical model for 5-hydroxyflavone

Abstract

The photophysics of the 5-hydroxyflavone (5HF) molecule has been revised. Conversely to what has been hitherto reported, the proton-transfer fluorescence of 5HF has been recorded under xenon lamp excitation in cyclohexane, hexane, ethanol, ethyl ether, 2-methyl-2-propanol, and dimethylsulfoxide at room temperature. The 5HF fluorescence spectra only exhibit one emission band centered at ca. 700 nm. A small photoreaction quantum yield of 10(-5)-10(-6) denotes the great photostability exemplified by 5HF in hydrocarbon solvent, ethanol, and dimethylsulfoxide. This great photostability is predominantly explained owing to an internal conversion process from the first excited singlet state 1(pi,pi*)1 (S1), which has a repulsive (proton-transfer) potential energy curve with respect to the stretching of the OH bond and only one energy minimum for the proton-transfer tautomer. The S1'-S0' energy gap proves to be small because of important modifications found in the molecular geometry of 5HF upon photoexcitation. A computational strategy, based upon theoretical calculations at the B3LYP density functional theory (DFT) and time-dependent DFT levels, supports the experimental spectroscopic evidence. Also an abnormal singlet-triplet splitting for a pi,pi* configuration has been found in 5HF.