Abstract
A molecular design approach was used to create asymmetrical visible light-triggered azo-derivatives that can be good candidates for polymer functionalization. The specific electron–donor substituted molecules were characterized and studied by means of NMR analyses and UV-visible spectroscopy, comparing the results with Time Dependent Density Functional (TD-DFT) calculations. A slow rate of isomerization (ki = 1.5 × 10−4 s−1) was discovered for 4-((2-hydroxy-5methylphenyl) diazenyl)-3-methoxybenzoic acid (AZO1). By methylating this moiety, it was possible to unlock the isomerization mechanism for the second molecule, methyl 3-methoxy-4-((2-methoxy-5-methylphenyl) diazenyl)benzoate (AZO2), reaching promising isomerization rates with visible light irradiation in different solvents. It was discovered that this rate was heightened by one order of magnitude (ki = 3.1 × 10−3 s−1) for AZO2. A computational analysis using density functional (DFT/PBE0) and wavefunction (QD-NEVPT2) methodologies provided insight into the photodynamics of these systems. Both molecules require excitation to the second (S2) excited state situated in the visible region to initiate the isomerization. Two classic mechanisms were considered, namely rotation and inversion, with the former being energetically more favorable. These azo-derivatives show potential that paves the way for future applications as building blocks of functional polymers. Likewise, they could be really effective for the modification of existing commercial polymers, thus transferring their stimuli responsive properties to polymeric bulky structures, converting them into smart materials.
Highlights
A great attention during the past decades has been addressed to photochromic molecules in the field of materials science
These organic compounds can be included in many materials, changing the properties of the system when irradiated with light of the appropriate wavelength
Molecular Design of the Azo-derivatives: Azo compounds are usually synthesized with procedures like: azo coupling reaction, Mills reaction and Wallach reaction [46]
Summary
A great attention during the past decades has been addressed to photochromic molecules in the field of materials science These organic compounds can be included in many materials, changing the properties of the system when irradiated with light of the appropriate wavelength. Polymers 2019, 11, x FOR PEER REVIEW affect characteristics like: electronic or ionic conductivity, fluorescence, magnetism, shape, and procedures, good processability, as well as high thermal and are chemical stability[1][7]. The most studied photochromic molecules azobenzenes which have been interesting characteristic of azobenzene molecules is their reversible isomerization of the double widely investigated as promising photo-switchers [2,3,4,5,6] due to their simple preparation procedures,bond, between thermally stable
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