2,4-Dihydroxybenzophenone is the most widely used molecule in the benzophenone group of UV absorbers. It is known that the UV absorption ability is dependent on the substituents. Numerous studies have shown that the strength of intramolecular hydrogen bonds is the main factor affecting this type of UV absorber. However, the effect of substituents on the formation and nature of the hydrogen bonds has not been well studied. In this work, the effect of the type of substituent and the substitution position on the absorption intensity of 2,4-dihydroxybenzophenone molecules is verified both experimentally and theoretically. The effect of substituents on the intramolecular hydrogen bonding of 2,4-dihydroxybenzophenone was investigated by DFT calculations. The results indicate that the addition of different substituents leads to various changes in the strength of the hydrogen bonding in 2,4-dihydroxybenzophenone. On the X-substitution site or the Y-substitution site, halogen groups and electron-absorbing groups such as -CN and -NO2 increase the strength of the hydrogen bond, while electron-giving groups such as -N(CH3)2 and -OCH3 decrease the strength of the bond. For the same substituent, the one at the Y site has a higher effect on hydrogen bonding than that at the X site. By NBO analysis, it was found that the substituents would cause charge redistribution of the individual atoms of 2,4-dihydroxybenzophenones, thus affecting the formation and strength of the hydrogen bonds. Moreover, when the substituent is at the Y substitution site, the oxygen atom of the carbonyl group is less able to absorb electrons and more charge is attracted to the oxygen atom of the hydroxyl group, resulting in a larger charge difference between the two oxygen atoms and an increase of bond energy. Finally, a multiple linear regression analysis of the NPA charge number of the atoms involved in the formation of the hydrogen-bonded chelated six-membered ring was performed with the energy of the hydrogen bond and the percentage of influencing factors estimated, which were found to jointly affect the strength of hydrogen bonding. The aim of this study is to provide theoretical guidance for the design of benzophenone-based UV absorbers that absorb UV light of specific wavelength bands.
Keywords: 2,4-dihydroxybenzophenone; density functional theory; hydrogen bonding; substituents.