Mechanochemical Fabrication of Full-Color Luminescent Materials from Aggregation-Induced Emission Prefluorophores for Information Storage and Encryption

The development of luminescent materials via mechanochemistry embodies a compelling yet intricate frontier within materials science. Herein, we delineate a methodology for the synthesis of brightly luminescent polymers, achieved by the mechanochemical coupling of aggregation-induced emission (AIE) prefluorophores with generic polymers. An array of AIE moieties tethered to the 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical are synthesized as prefluorophores, which initially exhibit weak fluorescence due to intramolecular quenching. Remarkably, the mechanical coupling of these prefluorophores with macromolecular radicals, engendered through ball milling of generic polymers, leads to substantial augmentation of fluorescence within the resultant polymers. We meticulously evaluate the tunable emission of the AIE-modified polymers, encompassing an extensive spectrum from the visible to the near-infrared region. This study elucidates the potential of such materials in stimuli-responsive systems with a focus on information storage and encryption displays. By circumventing the complexity inherent to the conventional synthesis of luminescent polymers, this approach contributes a paradigm to the field of AIE-based polymers with implications for advanced technological applications.


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19.6 mL (0.18 mol) respectively.Subsequently, 1 mL (3 mmol) of Methacrylic anhydride was added to the resulting solution (referred to as Solution A).Additionally, 10 mg of the fluorescent polymer was dissolved in 1 mL of chlorine dioxide (Solution B).Solution A and Solution B were mixed together and stored in a light-protected environment.A Digital Light Processing (DLP) 3D printing system equipped with a 405-nm LED Wavelength (Asiga Max X27) was used at a temperature of 30 ℃ to fabricate multi-color fluorescent capital characters.The samples were printed with a Z layer thickness of 0.050 mm and an exposure time of 2.7 s, while burn-in layers were exposed for 13 s.To remove any uncured resin, the specimens were immersed in absolute ethyl alcohol and subjected to ultrasound for 10 minutes.Subsequently, they were post-cured at room temperature for 20 minutes using a 405 nm light source.
Mobile Phone Applications.The scan software utilized in this study is COLORCODE® (http://colorzip.com).At the time of publication, this information reading application was accessible for free to conduct code scanning, but the authors are unaware of its availability for any other purpose.

Figure 23 .
Figure 23.FMO energy diagrams of deactivation mechanism.The ESSR denotes excites state structure relaxation.

Figure 24 .Figure 25 .Figure 26 .
Figure 24.Molecular orbitals for the corresponding electronic transitions of B-tp at the optimized ground D0 state conformation. of the B-tp at ground state.

Figure 27 .
Figure 27.Molecular orbitals for the corresponding electronic transitions of B-tp-H at the optimized excited S1 state conformation.

Figure
Figure S30.a) Absorption and b) emission spectra of fluorescent B-PSs obtained by PS samples from different synthetic methods (AIBN and BPO as initiators for freeradical polymerization)

Figure S31 .Figure S32 .
Figure S31.Calibration curve for the fluorescence intensity of B-tp-H as a function of its concentration in dilute toluene.

Figure S33 .
Figure S33.Normalized PL spectra of the obtained fluorescent PMMA.

Figure S34 .Figure S35 .
Figure S34.Photographs of PMMA and AIE pre-fluorophores-attached PMMA under daylight and UV light.

Figure S36 .
Figure S36.Normalized PL spectra of the obtained fluorescent PPS.

Table S1 .
Mn and PDI of polymer samples before and after ball milling in the presence of AIE pre-fluorophores a Determined by GPC in THF, based on linear PS as a calibration standard.

Table S2 .
The amount of dye incorporated within the polymer after ball milling.

Table S3 .
Photoluminescence quantum yield (PLQY) of the AIE pre-fluorophores and the AIE pre-fluorophores-attached polymersTable S4 Photophysical parameters of AIE pre-fluorophores and the AIE pre- a The wavelength of absorption maximum in the solid state b The wavelength of emission maximum in the solid state c Lifetime determined the solid state at room temperature