Substituent effects in 2-hydroxybenzophenone-based ultraviolet absorbers

Abstract

2-Hydroxybenzophenone is the simplest molecule among benzophenone-based UV absorbers. Changing the position and type of substituents affects the strength of intramolecular hydrogen bonding and thus modulates the UV absorption properties. In this work, 132 2-hydroxybenzophenone-based UV absorbers with different substituent positions and species were designed to investigate the substituent effect in their UV absorption properties. The results show that when the substituent positions are the same, the characteristic peaks of the compounds containing substituents of the same group of atoms or homologous groups correspond to similar wavelengths. When the substituent groups are the same, the wavelength redshift of the characteristic peaks of the UV absorption spectra of the compounds of the NX and NZ classes is more pronounced than that of the remaining species, and the substituent group containing N atoms causes the molecule to have a more pronounced wavelength redshift. The redshift of the characteristic absorption peaks corresponding to the wavelengths decreases with the increase of the energy level difference. Atoms-in-molecules (AIM) analysis showed that the electron-absorbing group in the compound enhances the hydrogen bond strength to a lesser extent than the electron-donating group. Natural Bond Orbital (NBO) analysis further revealed that the type and position of the substituent groups in the molecular structure influenced the strength of the intramolecular hydrogen bonding by affecting the distribution of the charges among individual atoms in the 2-hydroxybenzophenone molecules. This work aims to reveal the effect of substituents on the UV absorption properties of 2-hydroxybenzophenone-based molecules and to provide theoretical guidance for the design of such UV absorber molecules absorbing UV light at specific wavelengths.