Theoretical Study on Photothermal Properties of Azobenzene Sulfonate/Magnesium-Aluminum Hydroxide Composite Dye

Peihuan Zhang; Yue Zhu; Zhewei Li; Luocong Wang; Caiwei Yue; Ming Lei; Min Pu

doi:10.1021/acsomega.3c00791

Theoretical Study on Photothermal Properties of Azobenzene Sulfonate/Magnesium-Aluminum Hydroxide Composite Dye

ACS Omega. 2023 Mar 14;8(12):11596-11606. doi: 10.1021/acsomega.3c00791. eCollection 2023 Mar 28.

Authors

Peihuan Zhang¹, Yue Zhu¹, Zhewei Li¹, Luocong Wang¹, Caiwei Yue¹, Ming Lei¹, Min Pu¹

Affiliation

¹ State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Institute of Computational Chemistry, Beijing University of Chemical Technology, Beijing 100029, P. R. China.

Abstract

The assembly of various azo dyes and pigments with inorganic layered materials could develop new types of intercalation materials. The electronic structures and photothermal properties of composite materials (AbS^--LDH) constituted by azobenzene sulfonate anions (AbS^-) and Mg-Al layered double hydroxide (LDH) lamella were theoretically studied at the M06-2X/def2-TZVP//M06-2X/6-31G(d,p) level using density functional theory and time-dependent density functional theory. Meanwhile, the influences of LDH lamella on the AbS^- in AbS^--LDH materials were investigated. The calculated results showed that the addition of LDH lamella could lower the isomerization energy barrier of CAbS^- anions (CAbS^- stands for cis AbS^-). The thermal isomerization mechanisms of AbS^--LDH and AbS were related to the conformational change of the azo group, out-of-plane rotation and in-plane inversion. The LDH lamella could reduce the energy gap of the n → π* and π → π* electronic transition and lead to a red-shift in the absorption spectra. When a polar solvent DMSO was applied, the excitation energy of the AbS^--LDHs was increased, making its photostability stronger than in nonpolar solvent and solvent-free.