A polymer-based room-temperature phosphorescent material based on dynamic covalent bonds and a preparation method and application thereof

Abstract

This invention belongs to the field of organic light-emitting materials technology, specifically relating to a polymer-based room-temperature phosphorescent material based on dynamic covalent bonds, its preparation method, and its applications. The polymer-based room-temperature phosphorescent material of this invention exhibits reversible ammonia / thermal stimulation responsiveness and can serve as a highly efficient triplet donor, achieving chiral multicolor afterglow through TS-FRET, thereby supporting multi-level information storage and anti-counterfeiting encryption.

Description

Technical Field

[0001] This invention belongs to the field of organic light-emitting materials technology, specifically relating to a polymer-based room-temperature phosphorescent material based on dynamic covalent bonds, its preparation method, and its application. Background Technology

[0002] Polymer-based room-temperature phosphorescent (RTP) materials possess unique advantages in applications such as anti-counterfeiting and information encryption. As application demands evolve from single-emission output to multi-dimensional information encoding, there is a pressing need for synergistic optimization of multiple performance indicators, including afterglow lifetime, quantum efficiency, environmental stability, color tunability, and responsiveness to external stimuli. In particular, further incorporating circularly polarized emission (CPL) into polymer-based RTP systems, i.e., achieving circularly polarized room-temperature phosphorescence (CP-RTP), holds promise for simultaneously improving information capacity and encryption levels. However, achieving persistent RTP, efficient CPL, and reversible stimulus responsiveness within a single polymer RTP system remains a significant challenge.

[0003] Mechanistically, the realization of persistent RTP depends not only on favorable intersystem crossing (ISC) to promote the generation of triplet excitons, but also on the effective suppression of nonradiative decay channels by a rigid microenvironment. Meanwhile, the generation of CP-RTP depends not only on intrinsic molecular chirality but also on chiral assembly within the local microenvironment. Therefore, combining luminescent framework design with luminescent-polymer interaction engineering is an effective strategy to simultaneously improve luminescent lifetime, quantum efficiency, chiral optical signal, and environmental stability in a single system. The luminescent framework determines the source of chirality, energy level distribution, conformational characteristics, and interaction sites, while luminescent-polymer interactions can modulate local rigidity / microenvironment and excited-state relaxation processes through hydrogen bonding, electrostatic interactions, π-π stacking, or dynamic covalent bonds, thereby synergistically regulating RTP, CPL, and stimulus-response behavior.

[0004] Furthermore, polyvinyl alcohol (PVA) possesses excellent film-forming properties, a dense hydrogen bond network, and good oxygen barrier properties, making it one of the most commonly used polymer matrices for constructing polymer-based afterglow systems. However, existing PVA-based RTP systems mainly focus on improving the RTP performance of achiral luminescent materials by modulating hydrogen bond interactions. Based on this, this paper proposes a novel luminescent material-polymer interaction engineering design strategy, providing new insights for the construction and functional expansion of polymer-based afterglow materials. Summary of the Invention

[0005] To address the problems existing in the prior art, the present invention aims to provide a polymer-based room-temperature phosphorescent material that combines persistent RTP, high-efficiency CPL, and reversible stimulus-responsiveness. The above objective is achieved primarily through the following technical solutions: A polymer-based room-temperature phosphorescent material based on dynamic covalent bonds, wherein an organic boron emitting element is doped into the polymer matrix through dynamic covalent bond interactions, and the organic boron emitting element is a compound represented by Formula I or Formula II, or its stereoisomers and geometric isomers; (I) (II); Where X and Y are independently selected from H, D, and C, respectively. 1-10 Alkyl, C 1-10 Alkoxy, C 1-10 Haloalkyl, C 1-10 Halogenated alkoxy groups; R1 through R8 are independently selected from H, D, F, Cl, Br, I, and C, respectively. 1-10 Alkyl, C 1-10 Alkoxy and C 1-10 Alkylthio, the C 1-10 Alkyl, C 1-10 Alkoxy and C 1-10 The alkylthio group can be independently and optionally replaced by substituents selected from D, F, Cl, Br and I; R9~ R 16 Each of the following is independently selected from H, D, F, Cl, Br, I, OH, NH2, CN, NO2, and C. 1-10 Alkyl, C 1-10 Alkoxy, C 1-10 alkylthio and C 1-10 Alkylsilyl, the C 1-10 Alkyl, C 1-10 Alkoxy, C 1-10 alkylthio and C 1-10 The alkylsilyl group can be independently and optionally replaced by substituents selected from D, F, Cl, Br and I.

[0006] In some embodiments, X and Y are independently selected from H, D, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, -CHF2, -CF3, -CHFCH2F, -CF2CHF2, -CH2CF3, -CH2CF2CHF2, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, -OCHF2, -OCF3, -OCHFCH2F, -OCF2CHF2, -OCH2CF3, or -OCH2CF2CHF2.

[0007] In some embodiments, R1 to R8 are independently selected from H, D, F, Cl, Br, I, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, -CHF2, -CF3, -CHFCH2F, -CF2CHF2, -CH2CF3, -CH2CF2CHF2, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, -OCHF2, -OCF3, -OCHFCH2F, -OCF2CHF2, -OCH2CF3, or -OCH2CF2CHF2.

[0008] In some implementation schemes, R9~R 16 Each of the following is independently selected from H, D, F, Cl, Br, I, OH, NH2, CN, NO2, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, -CHF2, -CF3, -CHFCH2F, -CF2CHF2, -CH2CF3, -CH2CF2CHF2, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, -OCHF2, -OCF3, -OCHFCH2F, -OCF2CHF2, -OCH2CF3, or -OCH2CF2CHF2.

[0009] In some embodiments, the organoboron luminescent material is one of the following compounds and their stereoisomers and geometric isomers: , , , , , , , , , , or .

[0010] In some embodiments, the polymer matrix is ​​polyvinyl alcohol, polymethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, or polyacrylic acid.

[0011] On the other hand, the present invention also protects a method for preparing the above-mentioned polymer-based room temperature phosphorescent material, comprising the following steps: The polymer matrix is ​​added to deionized water and stirred until completely dissolved. Then, an organic boron luminescent agent and an alkali are added and stirred until homogeneous to obtain a mixed solution. The mixed solution is then dropped onto the surface of the substrate material and evaporated to obtain a polymer-based room temperature phosphorescent material.

[0012] In some embodiments, the organic solution is selected from one or more of DMF, DMSO, ethanol, methanol, tetrahydrofuran, and acetone; the base is triethylamine or ammonia; and the substrate material is a coverslip or quartz.

[0013] In some embodiments, the mass ratio of the polymer matrix to the organoboron luminescent material is 1:(0.0001~0.001); the concentration of the organic solution of the organoboron luminescent material is 0.5~3 mg / mL.

[0014] On the other hand, the present invention also protects the application of the above-mentioned polymer-based room temperature phosphorescent materials in the fields of information encryption, flexible display and anti-counterfeiting labeling.

[0015] Compared with the prior art, the present invention achieves the following beneficial effects: 1) This invention uses a binaphthalene-organoboron luminescent material. R / S -BBO and R / S Using -BBOH as the emitter guest and PVA as the polymer matrix, three types of doped PVA systems with progressively enhanced emitter-polymer interactions were constructed, progressing from weak non-covalent interactions and strong hydrogen bonding to dynamic covalent confinement. The results show that as the emitter-polymer interaction strengthens, the system's local rigidity, network confinement effect, and triplet stability continuously improve, while molecular motion and non-radiative decay are effectively suppressed, thus achieving a synergistic enhancement of RTP and CPL performance.

[0016] 2) Benefiting from the covalent confinement mediated by dynamic boronic acid ester bonds, R The -BBOH-PVA system exhibits the best luminescence performance: its phosphorescence lifetime reaches 967.51 ms, and its phosphorescence quantum yield is 5.73%. lum 3.9 × 10 -3 It also exhibits a recognizable CP-RTP signal. This is because the covalent anchoring of borate esters not only significantly enhances the rigidity of the local microenvironment and stabilizes the triplet exciton, but may also enhance the SOC associated with the ISC process and phosphorescence emission.

[0017] 3) R The -BBOH-PVA system also exhibits reversible ammonia / thermal stimulus responsiveness and can serve as a highly efficient triplet donor to achieve chiral multicolor afterglow via TS-FRET, thereby supporting multi-level information storage and anti-counterfeiting encryption. The luminescent material-polymer engineering strategy proposed in this invention provides important guidance for optimizing the luminescent performance of polymer-based RTP materials. Attached Figure Description

[0018] Figure 1 For compounds R -BBO 1H NMR spectrum.

[0019] Figure 2 For compounds S -BBO 1 H NMR spectrum.

[0020] Figure 3 For compounds R -BBOH 1 H NMR spectrum.

[0021] Figure 4 For compounds S -BBOH 1 H NMR spectrum.

[0022] Figure 5 For compounds R The photophysical properties of -BBOH are shown in the following spectra: (a) R -BBOH in THF solution (10 -5 (b) UV–Vis absorption spectrum in M); R -BBOH in a dilute solution at 77 K (THF, 10) -5 Instantaneous and delayed PL spectra in M); (c) R -BBOH in a dilute solution at 77 K (THF, 10) -5 The time-resolved phosphorescence decay curves in (M) (λex = 320 nm, monitoring wavelength 554 nm); (d) R Normalized photoluminescence spectrum of -BBOH in solid state and delayed photoluminescence spectrum at room temperature.

[0023] Figure 6 For compounds R -BBO photophysical properties correlation spectrum, where (a) R -BBO in THF solution (10 -5 (M) and the excitation spectrum in the solid state; (b) R -BBO in THF solution (10 -5 The photoluminescence spectrum in M), and the delayed PL spectrum at 77 K; (c) R -BBO at 77 K, THF solution (10 -5 The time-resolved phosphorescence decay curves in (M); (d) R Instantaneous and delayed PL spectra of -BBO in solid state.

[0024] Figure 7 For doped PVA thin films R -BBO@PVA R-BBOH@PVA and R Photophysical properties of BBOH-PVA are shown in Figure 1, where (a) instantaneous and delayed PL spectra; (b) time-resolved phosphorescence decay curves; (c) CD and UV-vis absorption spectra; (d) CPL and DC spectra; and (e) luminescence photographs at different durations after UV irradiation (254 nm) and removal of UV light.

[0025] Figure 8 For doped PVA thin films R -BBO@PVA R -BBOH@PVA and R Photophysical properties of -BBOH-PVA, spectral data 2, including: (a) RTP intensity versus time under acid / alkali fumigation treatment; (b) RTP intensity versus time under ammonia / heating cycle treatment; (c) Luminescence photographs under ammonia / heating cycle treatment; (d) RTP intensity versus temperature under heating treatment; (e) RTP intensity variation under different heating temperatures; and (f) Luminescence photographs after UV light irradiation (254 nm) was turned off at different temperatures.

[0026] Figure 9 For the TS-FRET system RhB@ R -BBOH-PVA and Cy5@ R Photophysical properties of BBOH-PVA, including (a) and (e) superimposed spectra of donor fluorescence / phosphorescence emission and acceptor absorption / fluorescence emission; (b) and (f) concentration-dependent delayed emission spectra; (c) and (g) time-resolved phosphorescence decay curves of the donor; (d) and (h) time-resolved delayed fluorescence decay curves of the acceptor; (i) CD and UV–vis absorption spectra; (j) CPL and DC spectra; and (k) a simplified Jablonski energy level diagram used to describe the TS-FRET process.

[0027] Figure 10 A diagram related to information encryption and anti-counterfeiting applications, wherein (a) writable ink R (a) Schematic diagram and photograph of BBOH-PVA; (b) By R -BBOH-PVA, RhB@ R -BBOH-PVA and Cy5@ R (c) A colorful encrypted pattern constructed from BBOH-PVA; R Schematic diagram of NH3·H2O / thermal erasure type encryption pattern prepared by -BBOH-PVA.

[0028] Figure 11 for R -BBO@PVA R -BBOH@PVA and R Schematic diagram of the preparation, luminescent properties, and luminescent-polymer interaction analysis of the -BBOH-PVA doped PVA system (τ) P Phosphorescence lifetime; Φ P (Phosphorus quantum yield). Detailed Implementation

[0029] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0030] The endpoints and any values ​​of the ranges described in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. The raw materials and reagents used in the following examples are commercially available.

[0031] 1 H NMR and 13 C10 NMR spectra were measured on a BRUKER AMX 500 MHz instrument and a Bruker AVANCENEO 101 MHz instrument, with tetramethylsilane as an internal standard.

[0032] Molecular mass was determined by mass spectrometry (Xevo G2-XS QTof) and MALDI-TOF MS (Bruker Autoflex maX). The UV–Vis absorption spectra of the compounds were measured using a Perkin Elmer Lambda 365. Instantaneous, delayed, and transient decay spectra were measured on Edinburgh Instruments (FLS 1000); All phosphorescence emission spectra were measured with a delay time of 3 ms. Low-temperature (77 K) phosphorescence testing was performed using liquid nitrogen. Absolute PLQY was determined using a Hamamatsu quantum yield spectrometer (C11347); Fluorescence and phosphorescence images of the crystals were taken using a Canon camera; Circular dichroism (CD) spectra were acquired on an Applied Photophysics Chirascan, and circularly polarized emission (CPL) spectra were measured using a JASCO CPL-300 spectrometer.

[0033] Related terms: RTP: Room temperature phosphorescence; CPL: Circularly polarized emission; CP-RTP: Circularly polarized room temperature phosphorescence; ISC: Intersystem crossing; SOC: Spin-orbit coupling; TS-FRET: Triple-state sensitized Förster resonance energy transfer; PVA: Polyvinyl alcohol; CD: Circular dichroism; g lum : Luminescence asymmetry factor.

[0034] Preparation Example 1 R / S -BBO and R / S Synthesis of -BBOH

[0035] 1) R Synthesis of -BBr ( R 6,6'-dibromo-[1,1'-binaphthyl]-2,2'-diol (3.00 g, 6.75 mmol), diiodomethane (5.43 g, 20.26 mmol), and K₂CO₃ (5.60 g, 40.53 mmol) were dissolved in 50 mL of acetone and refluxed overnight at 50 °C. After cooling to room temperature, the crude product was extracted with dichloromethane, washed successively with deionized water and saturated brine, and dried over anhydrous sodium sulfate. After filtration and solvent removal, the product was purified by silica gel column chromatography with PE / DCM = 10 / 1 (v / v) to give a white solid in 80% yield (2.47 g).

[0036] 1 H NMR (500 MHz, Chloroform- d ) δ 8.11 (s, 2H), 7.90 (d, J = 8.8 Hz,2H), 7.50 (d, J = 8.7 Hz, 2H), 7.38 (d, J = 9.3 Hz, 2H), 7.31 (d, J = 8.8 Hz,2H), 5.69 (s, 2H). MS [m / z]: calcd for C 21 H 12Br2O2, 453.9204; found, 453.9196. 2) S Synthesis of -BBr S Synthesis methods of -BBr and R -BBr is similar, to ( R Replace 6,6'-dibromo-[1,1'-binaphthyl]-2,2'-diol with ( S 6,6'-dibromo-[1,1'-binaphthyl]-2,2'-diol (3.00 g, 6.75 mmol). The product was a white solid (2.62 g, 85%).

[0037] 1 H NMR (500 MHz, Chloroform- d ) δ 8.10 (s, 2H), 7.90 (d, J = 8.7 Hz,2H), 7.50 (d, J = 8.7 Hz, 2H), 7.38 (d, J = 9.1 Hz, 2H), 7.31 (d, J = 9.2 Hz,2H), 5.69 (s, 2H). MS [m / z]: calcd for C 21 H 12 Br2O2, 453.9204; found, 453.9195. 3) R Synthesis of -BBO Will R 1,4-Dioxane (500 mg, 1.10 mmol), palladium catalyst PdCl2 (dppf) (96.25 mg, 0.13 mmol), KOAc (1.29 g, 13.15 mmol), and diboron reagent (1.22 g, 4.82 mmol) were added to a flask under nitrogen protection. Then, 1,4-dioxane (15 mL) was added, and the mixture was refluxed, with the reaction monitored by TLC. After cooling to room temperature, the mixture was filtered and the solvent removed under reduced pressure. The residue was purified by silica gel column chromatography with PE / DCM as the eluent, repeated three times, yielding a white powder; further purification by recrystallization yielded a white product (500.64 mg, 83%).

[0038] 1 H NMR (400 MHz, Chloroform- d) δ 8.45 (s, 2H), 8.02 (d, J = 8.7 Hz, 2H), 7.63 (dd, J = 8.5, 1.3 Hz, 2H), 7.45 (dd, J = 11.4, 8.6 Hz, 4H), 5.70(s, 2H), 1.38 (s, 24H). 13 C NMR (101 MHz, CDCl3) δ 152.30, 136.79, 133.93, 131.26, 130.79,126.14, 126.05, 121.04, 103.29, 84.07, 77.48, 77.16, 76.84, 25.10, 25.01. MS [m / z]: calcd for C 33 H 36 B2O6, 550.2816; found, 550.2743. 4) S Synthesis of -BBO S The synthesis method of -BBO and R -BBO is the same, will R -BBr replaced with S -BBr (500 mg, 1.10 mmol) yielded a white product (494.61 mg, 82%).

[0039] 1 H NMR (400 MHz, Chloroform- d ) δ 8.45 (s, 2H), 8.02 (d, J = 8.7 Hz, 2H), 7.64 (dd, J = 8.5, 1.3 Hz, 2H), 7.45 (t, J = 8.8 Hz, 4H), 5.70 (s, 2H), 1.37 (s, 24H). 13 C NMR (101 MHz, CDCl3) δ 152.29, 136.79, 133.92, 131.25, 130.78,126.12, 126.04, 121.03, 103.28, 84.05, 77.48, 77.16, 76.84, 25.09, 25.00. MS [m / z]: calcd for C 33 H 36B2O6, 550.2816; found, 550.2759. 5) R Synthesis of -BBOH Will R -BBO (300 mg, 0.55 mmol) and methylboronic acid (261.08 mg, 4.36 mmol) were dissolved in trifluoroacetic acid solution [5% (v / v) in dichloromethane, approximately 10 mL / mmol], and stirred overnight at room temperature. After the reaction was complete, all volatile components were evaporated off under a 40 °C water bath. To avoid the formation of mixed anhydrides, the residue was redissolved in 0.N HCl (approximately 10 mL / mmol), then evaporated to dryness and dried under vacuum to give the target product (128.36 mg, 64%).

[0040] 1 H NMR (500 MHz, Methanol-d4) δ 8.29 (s, 2H), 8.08 (d, J = 8.6 Hz, 2H), 7.51 (t, J = 8.6 Hz, 4H), 7.38 (d, J = 8.6 Hz, 2H), 5.68 (s, 2H), 3.35(s, 4H). MS [m / z]: calcd for C 21 H 16 B2O6, 386.1135; found, 386.1135. 6) S Synthesis of -BBOH S The synthesis method of -BBOH and R -BBOH is the same, and will R -BBO replaced with S -BBO (300 mg, 0.55 mmol). A white product (147.30 mg, 70%) was obtained.

[0041] 1 H NMR (500 MHz, Methanol-d4) δ 8.29 (s, 2H), 8.08 (d, J = 8.6 Hz,2H), 7.51 (t, J = 8.4 Hz, 4H), 7.38 (d, J = 8.5 Hz, 2H), 5.69 (s, 2H), 3.35(s, 4H). MS [m / z]: calcd for C 21 H 16B2O6, 386.1135; found, 386.1215.

[0042] 1) R -BBOH-PVA R -BBO-PVA S -BBOH-PVA and S Preparation of -BBO-PVA thin films 70 mg of PVA was added to 2.33 mL of deionized water and stirred at 85 °C for 1 h until completely dissolved. Then, while stirring, 200 μL of [unspecified ingredient] was simultaneously added to the prepared PVA solution. R A DMF solution of -BBOH (1 mg / mL) and 0.50 mL of ammonia were prepared. The resulting mixture was then stirred at 80 °C for 30 min. 1 mL of the aqueous solution was added dropwise to a clean coverslip and left at room temperature overnight to allow the water to evaporate; then it was heated at 80 °C until all the water had evaporated, yielding the desired product. R -BBOH-PVA film.

[0043] Prepared using a similar method R -BBO-PVA S -BBOH-PVA and S -BBO-PVA film.

[0044] 2) R -BBOH@PVA、 R -BBO@PVA S -BBOH@PVA and S Preparation of -BBO@PVA thin films In the above R -BBOH-PVA R -BBO-PVA S -BBOH-PVA and S Based on the preparation method of -BBO-PVA film, ammonia water is omitted to obtain... R -BBOH@PVA、 R -BBO@PVA S -BBOH@PVA and S -BBO@PVA film.

[0045] like Figures 5-6 As shown, R -BBO and R-BBOH exhibits only deep blue fluorescence at room temperature, both in THF solution and in the solid state, but displays phosphorescence with a clear vibrational fine structure in THF solution at 77 K. This indicates that although the covalently locked binaphthyl framework and organoboron units confer the luminescence... R / S -BBO and R / S -BBOH has the potential for triplet emission, but nonradiative relaxation dominates at room temperature, thus preventing the generation of RTP.

[0046] This invention investigates the effect of luminescent-polymer interactions on luminescence behavior. For example... Figure 7 As shown in a, R -BBO@PVA R -BBOH@PVA and R The steady-state and delayed emission spectra of the three types of PVA films—BBOH-PVA, etc.—are basically consistent: a fluorescence peak appears at approximately 375 nm, and well-resolved phosphorescent bands appear at 516, 554, and 596 nm. These phosphorescent bands are consistent with the low-temperature emission behavior of the luminescent material in THF solution at 77 K. This indicates that the polymer matrix mainly provides a rigid confined microenvironment for stabilizing triplet excitons, while different interaction modes do not change the emission origin, but mainly affect the excited-state stability and decay kinetics.

[0047] As the luminescent-polymer interaction gradually strengthens, the RTP lifetime increases from 233.40 ms to 432.06 ms, and further to 967.51 ms. Figure 7 (b) Meanwhile, the phosphorescence quantum yield increased from 2.26% to 4.09%, and finally reached 5.73%. These results indicate that stronger luminescent-polymer interactions can more effectively limit non-radiative decay pathways. Figure 7 The visible afterglow photographs in e further confirm this trend: after UV excitation ceases, the brightness and duration of the afterglow are significantly increased as the luminescent-polymer interaction is enhanced.

[0048] In addition to enhanced RTP performance, the chiral optical signal is also amplified with increasing intensity of the luminescent-polymer interaction. For example... Figure 7 As shown in cd, all three types of PVA films exhibit mirror circular dichroism (CD) and CPL responses corresponding to their enantiomers, but there are significant differences in signal intensity. R The maximum luminescence asymmetry factor (g) of -BBOH-PVA lum ) Reached 3.9 × 10 -3 Significantly higher than R-BBOH@PVA 1.6 × 10 -3 as well as R -BBO@PVA 1.2 × 10 -3 This indicates that stronger luminescent-polymer interactions are more conducive to constructing a stable chiral microenvironment and amplifying chiral optical signals. It is worth noting that... R / S -BBOH-PVA exhibited a clear CPL signal in the fluorescence region of approximately 380 nm, and a resolvable delayed CPL response was also detected in the phosphorescence region of 516-596 nm, with a maximum g lum Approximately ±1.3 × 10 -3 This confirmed the generation of CP-RTP. In contrast, no obvious CP-RTP was detected in the other two non-covalent systems under the same testing conditions, which may be due to their weaker phosphorescence intensity and chiral emission signal.

[0049] In addition to significantly improving static luminescence performance, this invention further investigates the influence of strong luminescent material-polymer interaction on dynamic luminescence regulation. For example... Figure 8 As shown in a-8c, R -BBOH-PVA showed almost no change in RTP intensity after exposure to acetic acid vapor for 20 min, indicating good structural stability under mild acidic conditions. In contrast, hydrochloric acid (HCl) fumigation rapidly quenched RTP within a short time, accompanied by fluorescence loss and a color change from colorless to yellowish-brown. Unlike acid treatment, the luminescence change induced by ammonia (NH3·H2O) fumigation was reversible. This is because the adsorption and permeation of NH3 / H2O molecules disrupts the hydrogen bond network within the PVA matrix and the borate ester bonds between the luminescent group and the PVA matrix, thereby exacerbating nonradiative deactivation and leading to phosphorescence quenching. After subsequent heat treatment, the adsorbed NH3 / H2O molecules were removed, the rigid microenvironment and the constraint imposed by the dynamic covalent borate ester bonds were restored, and the RTP intensity almost returned to its initial level. Conversely, the physically doped system... R -BBOH@PVA exhibits an irreversible response under the same treatment conditions: after treatment with NH3·H2O vapor, its phosphorescence is difficult to recover to its initial level during subsequent heating. This difference indicates that the recoverability of covalently confined systems stems from reversible dynamic covalent borate bonds and the resulting structural memory effect, while physically doped systems relying on non-covalent interactions are more prone to luminescent migration, aggregation, or local phase separation, leading to irreversible microstructure reconstruction.

[0050] This invention also investigated the temperature response behavior of three types of doped PVA systems. For example... Figure 8 As shown in d-8f, as the temperature increases,R -BBO@PVA R -BBOH@PVA and R The phosphorescence intensity of -BBOH-PVA gradually decreases due to nonradiative relaxation caused by enhanced thermal motion. However, they exhibit significantly different phosphorescence decay rates: due to the stronger resistance of covalent borate bonds to thermal motion, R -BBOH-PVA exhibits a slower decay trend; while R -BBOH@PVA decays faster at higher temperatures due to the disruption of the hydrogen bond network; R -BBO@PVA, relying solely on weaker non-covalent interactions, exhibits the fastest decay during heating. These temperature response behaviors further demonstrate that the strength of the luminescent-polymer interaction is a key factor determining luminescence stability and environmental adaptability.

[0051] Considering R -BBOH-PVA possesses both persistent RTP and chiral optical properties, and this invention further explores its potential as a triplet donor. Using commercially available dyes RhB or Cy5 as singlet acceptors, this invention constructs a co-doped system based on triplet-sensitized Förster resonance energy transfer (TS-FRET). Figure 9 As shown in a-9b, the phosphorescence emission band of the donor and the absorption band of the acceptor RhB exhibit good spectral overlap, satisfying the prerequisite for efficient TS-FRET. With increasing acceptor concentration, both the transient fluorescence and delayed emission intensities of the acceptor increase, while the fluorescence and phosphorescence emission of the donor gradually decrease, indicating that efficient TS-FRET occurred in the system. The time-resolved decay curve of the delayed emission provides quantitative support for the TS-FRET process. With increasing acceptor concentration, the phosphorescence lifetime of the donor continuously shortens, indicating that triplet energy is efficiently transferred to the acceptor, with a transfer efficiency reaching up to 60.9% (…). Figure 9 c). In particular, the delayed emission lifetime of the receptor can be estimated to be several hundred milliseconds ( Figure 9 d). When Cy5 acts as a receptor, Cy5@ R The -BBOH-PVA doped system also exhibits a similar TS-FRET phenomenon, with a transfer efficiency as high as 63.6%. Figure 9 e-9h). Additionally, RhB@ R -BBOH-PVA and Cy5@ R The -BBOH-PVA system exhibited mirror-image CD and CPL responses in both the donor and acceptor emission regions (Figures 9i and 9j), indicating that the TS-FRET process not only supports long-lived energy transfer but also maintains an effective chiral microenvironment after acceptor introduction. Figure 9 k).

[0052] Based on doped systems R Based on the multidimensional luminescent properties exhibited by -BBOH-PVA, this invention investigated its application potential in information storage and anti-counterfeiting fields. The results are shown in […]. Figure 10 .first, R -BBOH-PVA doped films can be used directly as writable afterglow ink, exhibiting blue fluorescence under UV irradiation and yellow afterglow after UV irradiation is removed. Figure 10 a). By further introducing RhB or Cy5 as receptors, the pattern can exhibit continuous color changes (from blue to orange-red, and then to yellow) as ultraviolet light is switched on / off and over time, thereby significantly increasing information capacity and forgery difficulty. Figure 10 b). At the same time, by taking advantage of its reversible responsiveness to NH3·H2O, a rewritable photomask anti-counterfeiting mode can also be constructed to realize the reversible "erasure-rewrite" of information (Figure 10c).

[0053] The above embodiments are merely illustrative examples and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A polymer-based room-temperature phosphorescent material based on dynamic covalent bonds, characterized in that, Organic boron luminescent materials are doped into a polymer matrix through dynamic covalent interactions. The organic boron luminescent material is a compound represented by Formula I or Formula II, or its stereoisomers and geometric isomers. (AND), (II); Where X and Y are independently selected from H, D, and C, respectively. 1-10 Alkyl, C 1-10 Alkoxy, C 1-10 Haloalkyl, C 1-10 Halogenated alkoxy groups; R1 through R8 are independently selected from H, D, F, Cl, Br, I, and C, respectively. 1-10 Alkyl, C 1-10 Alkoxy and C 1-10 Alkylthio, the C 1-10 Alkyl, C 1-10 Alkoxy and C 1-10 The alkylthio group can be independently and optionally replaced by substituents selected from D, F, Cl, Br and I; R9~ R 16 Each of the following is independently selected from H, D, F, Cl, Br, I, OH, NH2, CN, NO2, and C. 1-10 Alkyl, C 1-10 Alkoxy, C 1-10 alkylthio and C 1-10 Alkylsilyl, the C 1-10 Alkyl, C 1-10 Alkoxy, C 1-10 alkylthio and C 1-10 The alkylsilyl group can be independently and optionally replaced by substituents selected from D, F, Cl, Br and I.

2. The polymer-based room-temperature phosphorescent material according to claim 1, characterized in that, X and Y are independently selected from H, D, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, -CHF2, -CF3, -CHFCH2F, -CF2CHF2, -CH2CF3, -CH2CF2CHF2, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, -OCHF2, -OCF3, -OCHFCH2F, -OCF2CHF2, -OCH2CF3 or -OCH2CF2CHF2.

3. The polymer-based room-temperature phosphorescent material according to claim 1, characterized in that, R1 to R8 are independently selected from H, D, F, Cl, Br, I, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, -CHF2, -CF3, -CHFCH2F, -CF2CHF2, -CH2CF3, -CH2CF2CHF2, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, -OCHF2, -OCF3, -OCHFCH2F, -OCF2CHF2, -OCH2CF3, or -OCH2CF2CHF2.

4. The polymer-based room-temperature phosphorescent material according to claim 1, characterized in that, R9~ R 16 Each of the following is independently selected from H, D, F, Cl, Br, I, OH, NH2, CN, NO2, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, -CHF2, -CF3, -CHFCH2F, -CF2CHF2, -CH2CF3, -CH2CF2CHF2, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, -OCHF2, -OCF3, -OCHFCH2F, -OCF2CHF2, -OCH2CF3, or -OCH2CF2CHF2.

5. The polymer-based room-temperature phosphorescent material according to claim 1, characterized in that, The organoboron luminescent material is the following compound and its stereoisomers and geometric isomers: , , , , , , , , , , or .

6. The polymer-based room-temperature phosphorescent material according to claim 1, characterized in that, The polymer matrix is ​​polyvinyl alcohol, polymethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, or polyacrylic acid.

7. A method for preparing the polymer-based room-temperature phosphorescent material according to any one of claims 1 to 6, characterized in that, Includes the following steps: The polymer matrix is ​​added to deionized water and stirred until completely dissolved. Then, an organic boron luminescent agent and an alkali are added and stirred until homogeneous to obtain a mixed solution. The mixed solution is then dropped onto the surface of the substrate material and evaporated to obtain a polymer-based room temperature phosphorescent material.

8. The preparation method according to claim 7, characterized in that, The organic solution is selected from one or more of DMF, DMSO, ethanol, methanol, tetrahydrofuran, and acetone; the base is triethylamine or ammonia; and the substrate material is a coverslip or quartz.

9. The preparation method according to claim 7, characterized in that, The mass ratio of polymer matrix to organoboron luminescent material is 1:(0.0001~0.001); the concentration of the organic solution of organoboron luminescent material is 0.5~3 mg / mL.

10. The application of a polymer-based room-temperature phosphorescent material as described in any one of claims 1-6 in the fields of information encryption, flexible display and anti-counterfeiting labeling.

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