Photochromic Polyurethane Coatings with Cross-Linked Structure and Self-Healing Behavior Based on the FRET Effect.

Intelligent fluorescent coatings have received widespread attention in the encryption technique field such as anti-counterfeit, while the traditional fluorescent coatings are easy to be damaged by external force. In this study, the fluorescent and self-healing anti-counterfeit coatings are prepared after rational molecular design. Two polymers containing fluorescent groups, including polyurethane containing the anthracene (AN) side group and polyimide containing the naphthalenediimide (NDI) structure are synthesized to realize multiple color changes with fluorescence through simply blending. Due to the overlapping fluorescence spectra of the groups, enabling the fluorescence resonance energy transfer effect (FRET), the coating with different group ratios exhibits tunable fluorescence under the same excitation light, providing diverse patterns. Moreover, due to the reversible photo-crosslinking and thermal de-dimerization properties of anthracene, the recording, erasure, and rewriting of the surface pattern can be realized, and the fluorescent anti-counterfeit coatings exhibit excellent self-healing properties after cross-linking due to the FRET effect, which solves the problem of poor healing and ensures the stability and integrity. The fluorescent coating with cross-linked structure and self-healing behavior based on the FRET effect greatly expands the functional applications of traditional polyurethane materials.

Mechanosynthesis of Photochromic Oligophenyleneimines: Optical, Electrochemical and Theoretical Studies.

In this work, two oligophenyleneimines type pentamers with terminal aldehydes, designated as DAFCHO (4,4'-((((((2,5-bis(octyloxy)-1,4-phenylene)bis(methanylylidene))bis(azanyl ylidene))bis(9H-fluorene-7,2-diyl))bis(azanylylidene))bis(methanylylidene))bis(2,5-bis(octyloxy) benzaldehyde)) and FDACHO (4,4'-((((((2,5-bis(octyloxy)-1,4-phenylene)bis(methanylylidene))bis (azanylylidene))bis(4,1-phenylene))bis(azanylylidene))bis(methanylylidene))bis(2,5-bis(octyloxy) benzaldehyde)) were synthesized by mechanochemistry method using 2,5-bis(octyloxy) terephtal aldehyde and 2,7-diaminofluorene or 1,4-phenylenediamine. All compounds were spectroscopically characterized using ¹H and 13C-NMR, FT-IR and mass spectrometry MALDITOF. The optical properties of the compounds were analyzed by UV-vis spectroscopy using different solvents. We observed that DAFCHO and FDACHO exhibit interesting photochromic properties when they are dissolved in chloroform and exposed to sunlight for 3, 5 and 10 min. The value of the energy band gap was calculated from the absorption spectra without irradiation Egap(optical). It was 2.50 eV for DAFCHO in chloroform solution, and it decreased to 2.34 eV when it is in films. For FDACHO, it was 2.41 eV in solution and 2.27 eV in film. HOMO (Highest Occupied Molecular Orbital), LUMO (Lowest Unoccupied Molecular Orbital) and Egap(electrochemical) values were obtained by electrochemical studies. The results indicate that the compounds can be considered as organic semiconductors since their values are 2.35 eV for DAFCHO and 2.06 eV for FDACHO. The structural and electronic properties of the compounds were corroborated with a DFT (Density Functional Theory) study.