Computational and experimental investigation of photoresponsive behavior of 4,4′-dihydroxyazobenzene diglycidyl ether

Abstract

The photochromic properties of 4,4′-dihydroxyazobenzene diglycidyl ether have been investigated to gain further insight into the photoisomerization pathways. The light induced trans–cis isomerization, thermal cis–trans recovery and light induced cis–trans isomerization were monitored using electronic absorption spectroscopy. The pohotoisomerization and thermal relaxation kinetics of azobenzene chromophores were investigated in solution. It was found that the trans–cis isomerization process occurs very fast and a high content of cis isomer was obtained (94 %). The optimization of the ground and transition state geometries as well as the electronic structure of the azo epoxy derivative was performed by the density functional theory (DFT) and time-dependent DFT with PBE0 and CAM-B3LYP functionals, using 6-31 + G(d,p) as basis set. Also, the theoretical UV–vis absorption spectra were calculated. The mechanism of isomerization along the S2, S1 and S0 energy levels has been described. It was shown how each internal coordinate contributes to the isomerization mechanism. TD-DFT and DFT methods revealed that modification of the NN bond length was the internal coordinate responsible for the trans to cis as well as cis to trans conversion.

Keywords

• Azobezene
• Photoisomerization
• TDDFT
• Kinetics
• Isomerization mechanism
• UV–vis absorption spectroscopy