Insight into fluorescence properties of 14 selected toxic single-ring aromatic compounds in water: Experimental and DFT study

? The fluorescence peak location of 14 compounds interpreted at protein-like region. ? The p-electron system inside aromatic ring contributes to the fluorophore region. ? Functional group variation effects the emission spectra. ? Decrease in quantum yield and increase in DE is due to atomic weight F>Cl>Br>I. ? Theoretically results are in line with experimental ones. Various single-ring aromatic compounds in water sources are of great concern due to its hazardous impact on the environment and human health. The fluorescence excitation-emission matrix (EEMs) spectrophotometry is a useful method to identify organic pollutants in water. This study provides a detailed insight into the fluorescence properties of the 14 selected toxic single-ring aromatic compounds by experimental and theoretical analysis. The theoretical analysis were done with Time-Dependent Density Functional Theory (TD-DFT) and B3LYP/6-31G (d,p) basis set, whereas, Polarizable Continuum Model (PCM) was used to consider water as solvent. The selected compounds displayed their own specific excitation-emission (Ex/Em) wavelengths region, at Ex<280 nm and Em<340 nm, respectively. Whereas the theoretical Ex/Em was observed as, Ex at 240 nm–260 nm and Em at 255 nm–300 nm. Aniline as a strong aromatic base has longer Em (340 nm) than alkyl, carbonyl, and halogens substituted benzenes. The lone pair of electrons at amide substituent serves as a p-electron contributor into the aromatic ring, hence increasing the stability and transition energy, which results in longer emission and low quantum yield for the aniline. The fluorescence of halogenated benzenes illustrates an increase in the HOMO-LUMO energy gap and a decrease in quantum yield associated with atomic size (F>Cl>Br>I). In this study the theoretical results are in line with experimental ones. The understanding of fluorescence and photophysical properties are of great importance in the identification of these compounds in the water.