Thin film materials with photochromic and / or room temperature phosphorescent properties, methods of making and use thereof

Abstract

The application belongs to the field of functional materials, and particularly relates to a thin film material with photochromism and / or room-temperature phosphorescence as well as a preparation method and application thereof. The thin film material with photochromism and / or room-temperature phosphorescence is characterized by comprising a polymethyl methacrylate main body and a guest doped in the polymethyl methacrylate main body. Through a simple physical doping method, as preferred, two different optical response modes of radical-based photochromism and triplet-based photoactivated phosphorescence are realized in the same material. The synergistic effect of photoactivated phosphorescence and recyclable photochromism in the same thin film material breaks through the limitation of single function of existing materials and meets the demand of composite application in multiple scenes.

Description

Technical Field

[0001] This invention belongs to the field of functional materials, specifically relating to a thin film material with photochromic and / or room temperature phosphorescence, its preparation method, and its application. Background Technology

[0002] Photoresponsive materials, capable of undergoing reversible changes in physical or chemical properties under external light stimulation, represent the forefront of smart materials research. Among them, photochromic materials (color changes) and long-afterglow phosphorescent materials (luminescence changes) show great potential in fields such as anti-counterfeiting, encryption, and displays.

[0003] Currently, the following are the main problems in this technical field: (1) Functional limitation: Most reported materials only have a single photochromic or phosphorescent emission function. To achieve multiple anti-counterfeiting measures, it is usually necessary to physically mix or process multiple materials, which not only increases the complexity of the process, but may also lead to mutual interference of signals.

[0004] (2) Preparation complexity: Many high-performance materials, such as metal-organic frameworks (MOFs), covalent organic frameworks (COFs), or copolymers that require complex synthesis, have complicated preparation processes, harsh conditions, and high costs, making it difficult to achieve large-scale production and application.

[0005] (3) The contradiction between stability and processability: Small molecule photoresponsive materials are prone to aggregation in the solid state, which leads to fluorescence quenching or performance degradation, and it is difficult to directly process them into high-quality thin films. Although doping them into polymer matrices (such as PMMA) can improve processability, how to accurately control their optical properties and achieve dual response remains a challenge.

[0006] (4) Uncontrollable response mechanism: The photoresponse behavior of traditional materials (such as color change wavelength and emission color) is often determined by the molecules themselves. Once synthesized, it is difficult to adjust and there is a lack of a general strategy to flexibly customize the function of materials through simple molecular design.

[0007] Therefore, there is an urgent need and significant application value to develop a novel thin film material that is easy to prepare, has tunable performance, integrates multiple photoresponse functions, and has good stability. Summary of the Invention

[0008] The purpose of this invention is to provide a thin film material with photochromic properties and / or room temperature phosphorescence, as well as its preparation method and application.

[0009] To achieve the above objectives, the present invention adopts the following technical solution: A thin film material exhibiting photochromic and / or room-temperature phosphorescence comprises a polymethyl methacrylate (PMMA) host (I) and a guest doped in the PMMA host, the guest having a structure shown in the following formula: ; R1, R2, and R3 are independently naphthyl or phenanthryl; R1, R2, and R3 may be the same or different. Preferably, at least one of R1, R2, and R3 is different.

[0010] Preferably, the guest structure described in (II) is shown as 2,2,2-trinaphthylamine (II), 2,2-dinaphthyl-9-phenanthreneamine (III), 2-naphthyl-9,9-diphenanthreneamine (IV), 9,9,9-triphenanthreneamine (V); preferably, as shown in (III) and (IV); .

[0011] (II), (III), (IV), and (V) are prepared in the following manner: .

[0012] The doping amount of the object is 1-10%; preferably 5%.

[0013] The present invention also includes a method for preparing the aforementioned thin film material with photochromic and / or room temperature phosphorescence, comprising the following steps: S1. Weigh the polymethyl methacrylate (PMMA) matrix and place it in a clean, dry container. Add tetrahydrofuran solvent until completely dissolved to prepare a PMMA matrix solution; preferably, the PMMA matrix solution has a concentration of 100 mg / mL. S2. According to the doping ratio, measure the main PMMA solution from step S1 and dissolve the guest sample weighed in step S2. Disperse the sample evenly by ultrasonication until the sample is completely dissolved. After the solvent has completely evaporated, a thin film material with photostimulation response is obtained.

[0014] The present invention also includes the application of the aforementioned thin film material having photochromic and / or room temperature phosphorescence.

[0015] Preferred applications include anti-counterfeiting, information encryption and decryption, erasable materials, photochromic sunglasses, and 3D printing.

[0016] Compared with the prior art, the beneficial effects of the present invention are: 1. This invention designs naphthalene / phenanthrene-substituted triarylamine derivatives and achieves stepwise regulation of π-conjugation by adjusting the ratio of naphthalene and phenanthrene units. It establishes a quantitative relationship between "π-conjugation-photoresponse performance" and reflects the design of "molecular structure-performance", providing theoretical support for the customization of material performance.

[0017] 2. This invention, preferably through a simple physical doping method, achieves two distinct optical response modes in the same material: radical-based photochromism and triplet-state-based photoactivated phosphorescence. The synergistic effect of photoactivated phosphorescence and cyclic photochromism in the same thin film material overcomes the limitations of existing materials with single functions, meeting the needs of multi-scenario composite applications.

[0018] 3. The entire preparation process of this invention requires no complex synthesis, only physical blending and solution film formation. The process is simple, reproducible, low-cost, and easy to prepare on a large scale. The simplified film formation process significantly improves the process compatibility and environmental stability of the film, lowering the barrier to large-scale application.

[0019] 4. Based on the dual-mode photoresponse characteristics, this invention deeply integrates material properties with specific scenarios to develop innovative applications such as multi-level anti-counterfeiting, optical photochromic glasses, and 3D printing, thus expanding the application boundaries of triarylamine derivative-based photoresponse materials. Attached Figure Description

[0020] Figure 1 This is the 1H NMR spectrum of the guest molecule 2,2,2-trinaphthylamine in Example 2 of the present invention.

[0021] Figure 2 This is the 13C NMR spectrum of the guest molecule 2,2,2-trinaphthylamine in Example 2 of this invention.

[0022] Figure 3 This is the HPLC spectrum of the guest molecule 2,2,2-trinaphthylamine in Example 2 of the present invention.

[0023] Figure 4 This is the HRMS spectrum of the guest molecule 2,2,2-trinaphthylamine in Example 3 of the present invention.

[0024] Figure 5 This is the 1H NMR spectrum of the guest molecule 2,2-dinaphthyl-9-phenanthramine in Example 3 of this invention.

[0025] Figure 6 This is the 13C NMR spectrum of the guest molecule 2,2-dinaphthyl-9-phenanthramine in Example 3 of this invention.

[0026] Figure 7 This is the HPLC spectrum of the guest molecule 2,2-dinaphthyl-9-phenanthramine in Example 3 of the present invention.

[0027] Figure 8 This is the HRMS spectrum of the guest molecule 2,2-dinaphthyl-9-phenanthramine in Example 3 of this invention.

[0028] Figure 9This is the 1H NMR spectrum of the guest molecule 2-naphthyl-9,9-diphenanthreneamine in Example 4 of this invention.

[0029] Figure 10 This is the 13C NMR spectrum of the guest molecule 2-naphthyl-9,9-diphenanthreneamine in Example 4 of this invention.

[0030] Figure 11 This is the HPLC spectrum of the guest molecule 2-naphthyl-9,9-diphenanthreneamine in Example 4 of this invention.

[0031] Figure 12 This is the HRMS spectrum of the guest molecule 2-naphthyl-9,9-diphenanthreneamine in Example 4 of this invention.

[0032] Figure 13 This is the 1H NMR spectrum of the guest molecule 9,9,9-triphenanthramine in Example 5 of the present invention.

[0033] Figure 14 This is the 13C NMR spectrum of the guest molecule 9,9,9-triphenanthramine in Example 5 of this invention.

[0034] Figure 15 This is the HPLC spectrum of the guest molecule 9,9,9-triphenanthreneamine in Example 5 of this invention.

[0035] Figure 16 This is the HRMS spectrum of the guest molecule 9,9,9-triphenanthramine in Example 5 of the present invention.

[0036] Figure 17 This is the phosphorescence spectrum of the guest (III) and host (I) thin film materials before and after photoactivation in Embodiment 5 of the present invention.

[0037] Figure 18 These are photographs of the thin film materials prepared by doping the guest (II), (III), (IV), and (V) with the host (I) in Examples 2, 3, 4, and 5 of the present invention before and after photoactivation under ultraviolet light irradiation and under the condition of being turned off.

[0038] Figure 19 These are the phosphorescence spectra of thin film materials prepared by doping guest (II), (III), (IV), and (V) with host (I) in Examples 2, 3, 4, and 5 of this invention after being irradiated with ultraviolet light.

[0039] Figure 20 These are the phosphorescence decay curves of thin film materials prepared by doping guest (II), (III), (IV), and (V) with host (I) in Examples 2, 3, 4, and 5 of this invention after photoactivation.

[0040] Figure 21These are photographs of the photochromic process of the thin film materials of the object (III) and the subject (I) in embodiments 2, 3, 4, and 5 of the present invention before and after ultraviolet light irradiation.

[0041] Figure 22 This is the time-dependent absorption spectrum of the thin film materials of the guest (II) and the host (I) in Embodiment 10 of the present invention.

[0042] Figure 23 This is the photochromic absorption cycle spectrum of the thin film materials of the guest (II) and the host (I) in Embodiment 10 of the present invention.

[0043] Figure 24 This is the time-dependent absorption spectrum of the thin film materials of the guest (III) and the host (I) in Embodiment 11 of the present invention.

[0044] Figure 25 This is the photochromic absorption cycle spectrum of the thin film materials of the guest (III) and the host (I) in Embodiment 11 of the present invention.

[0045] Figure 26 This is the time-dependent absorption spectrum of the guest (IV) and host (I) thin film materials in Embodiment 12 of the present invention.

[0046] Figure 27 This is the photochromic absorption cycle spectrum of the guest (IV) and host (I) thin film materials in Embodiment 12 of the present invention.

[0047] Figure 28 This is the absorption spectrum of the guest (V) and host (I) thin film materials before and after ultraviolet lamp irradiation in Embodiment 9 of the present invention.

[0048] Figure 29 In Example 13 of this invention, a photochromic material with photostimulation response characteristics is applied to optical photochromic glasses.

[0049] Figure 30 This is a schematic diagram of the screen printing structure in Example 14 of the present invention, and the application of the prepared photochromic material to information encryption and decryption.

[0050] Figure 31 These are photographs of the photochromic process of the thin film materials of the object (III) and the subject (I) in Embodiment 15 of the present invention before and after ultraviolet light irradiation.

[0051] Figure 32 In Example 15 of this invention, a photochromic material with photostimulation response characteristics is applied to erasable and rewritable information.

[0052] Figure 33This is a schematic diagram of 3D printing in Example 16 of the present invention, and the application of the prepared photoactivated phosphorescent material to information anti-counterfeiting. Detailed Implementation

[0053] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be further described in detail below with reference to the accompanying drawings and preferred embodiments.

[0054] I. Preparation of thin film materials with photochromic and / or room temperature phosphorescence: Example 1: Preparation of solution of main molecule (I) polymethyl methacrylate (PMMA): Weigh 10 g of PMMA and place it in a dry and clean 250 mL round bottom flask. Add 100 mL of tetrahydrofuran solvent. Seal the mouth of the flask with a clean glass stopper to prevent solvent evaporation. After the sample is completely dissolved, a colorless and transparent solution with a concentration of 100 mg / mL is obtained.

[0055] Example 2: Synthesis of guest molecule (II) 2,2,2-trinaphthylamine:

[0056] 2,2-Dinaphthylamine (1.35 g, 5 mmol), 2-bromonaphthyl (1.24 g, 6 mmol), palladium acetate (56 mg, 0.25 mmol), tri-tert-butylphosphine (0.3 mL, 0.13 mmol), and potassium tert-butoxide (0.84 g, 7.5 mmol) were weighed into a 250 mL reaction flask, dried under vacuum for 0.5 h, and then 40 mL of anhydrous and oxygen-free toluene solvent was added. The mixture was heated to reflux under nitrogen protection and stirred for 12 h. After the reaction was completed, the mixture was washed with water and separated by silica gel column chromatography (eluent: petroleum ether: dichloromethane = 15:1) to obtain a pure white solid (II) (1.57 g, 79.3%). Figure 1 Show 1 H NMR (400 MHz, CDCl3) δ (ppm) 7.78 (dd, J = 12.2, 8.9 Hz, 2H), 7.63-7.56 (m, 1H), 7.52 (d, J = 2.3Hz, 1H), 7.46-7.35 (m, 3H). Figure 2 Show 13 C NMR (101 MHz, CDCl3) δ (ppm) 145.54,134.58, 130.44, 129.21, 127.77, 127.18, 126.52, 124.86, 124.84, 120.97. Figure 3 The HPLC chromatogram is shown. Figure 4 The HRMS (ESI) m / z calcd for C is shown. 30 H 22 N + (M+H) + 396.17075, found 396.17229. Weigh 5 mg of the guest (II) from step S1 and place it in a clean, dry container. Measure 1 mL of the main (I) solution from Example 1 and dissolve the sample weighed in step S2 at a doping ratio of 5% by mass. Disperse the solution uniformly by ultrasonication. After the solvent has completely evaporated, a thin film material with photostimulation response is obtained.

[0057] Example 3: Synthesis of guest molecule (III) 2,2-dinathyl-9-phenanthreneamine:

[0058] The synthesis of guest molecule (III) was the same as that of guest molecule (II), and after purification, a pale yellow solid (IV) (1.45 g, 65.1%) was obtained. Figure 5 Show 1 H NMR (400 MHz, CDCl3) δ (ppm) 8.75 (dd, J = 12.3, 8.3Hz, 2H), 8.13 (d, J = 8.2 Hz, 1H), 7.80-7.70 (m, 5H), 7.69-7.61 (m, 3H),7.61-7.55 (m, 1H), 7.55-7.49 (m, 2H), 7.48-7.29 (m, 9H). Figure 6 Show 13 C NMR (100MHz, CDCl3) δ (ppm) 145.85, 142.07, 134.24, 132.27, 132.02, 130.03, 129.64,129.32, 128.82, 128.14, 127.39, 126.91, 126.77, 126.41, 126.15, 124.93,124.14, 123.12, 122.92, 122.46, 118.04. Figure 7 The HPLC chromatogram is shown. Figure 8 This shows the HRMS (ESI) m / z calcd for C 34 H 24 N + (M+H) +446.18640, found 446.18518. Weigh 5 mg of guest molecule (III) from step S1 and place it in a clean and dry container; measure 1 mL of the main (I) solution from Example 1 and dissolve the sample weighed in step S2 with a doping ratio of 5% by mass. Disperse the sample evenly by ultrasonication. After the solvent has completely evaporated, a thin film material with photostimulation response is obtained.

[0059] Example 4: Synthesis of guest molecule (IV) 2-naphthyl-9,9-diphenanthreneamine:

[0060] 2-Naphthylamine (0.72 g, 5 mmol), 9-bromophenanthrene (2.83 g, 11 mmol), tris(dibenzylacetone)palladium (0.458 g, 0.5 mmol), tri-tert-butylphosphine (0.5 mL, 0.25 mmol), and potassium tert-butoxide (1.68 g, 15 mmol) were weighed into a 250 mL reaction flask, dried under vacuum for 0.5 h, and then 50 mL of anhydrous and oxygen-free toluene solvent was added. The mixture was heated to reflux under nitrogen protection and stirred for 12 h. After the reaction was completed, the mixture was washed with water and separated by silica gel column chromatography (eluent: petroleum ether: dichloromethane = 18:1) to obtain a white solid (IV) 1.50 g (60.5%). Figure 9 Show 1 H NMR (400 MHz, CDCl3) δ (ppm) 8.83-8.65 (m, 4H), 8.30 (d, J = 8.3 Hz, 1H), 8.19 (d, J = 8.3Hz, 1H), 7.74 (d, J = 9.4 Hz, 1H), 7.72-7.53 (m, 9H), 7.48 (d, J = 8.4 Hz, 3H), 7.44-7.26 (m, 5H), 7.07 (s, 1H). Figure 10 Show 13 C NMR (101 MHz, CDCl3) δ(ppm)147.92, 134.44, 132.48, 132.32, 132.21, 129.64, 129.27, 129.11, 128.30,127.66, 127.18, 127.08, 127.01, 126.97, 126.36, 125.55, 125.31, 124.98,124.56, 124.21, 123.36, 123.19, 122.71, 122.65. Figure 11 The HPLC chromatogram is shown. Figure 12 The HRMS(ESI) m / z calcd for C is shown. 38 H 26 N + (M+H) + 496.20205, found 496.19887. Weigh 5 mg of the guest molecule (IV) from step S1 and place it in a clean, dry container. Measure 1 mL of the main (I) solution from Example 1 and dissolve the sample weighed in step S2 at a doping ratio of 5% by mass. Disperse the solution uniformly by ultrasonication. After the solvent has completely evaporated, a thin film material with photostimulation response is obtained.

[0061] Example 5: Synthesis of guest molecule (V) 9,9,9-triphenanthreneamine:

[0062] The synthesis method of guest molecule (V) is the same as that of guest molecule (IV), and after purification, a pale yellow solid (IV) (0.69 g, 24.1%) is obtained. Figure 9 The 1H NMR (400 MHz, DMSO-) is shown. d 6) δ (ppm) 8.87-8.81 (m, 1H), 8.78 (d,J = 8.3 Hz, 1H), 8.29 (s, 1H), 8.27-8.20 (m, 1H), 7.95 (dd, J = 7.8, 1.6 Hz,1H), 7.79-7.61 (m, 4H); Figure 10 The 13C NMR (100 MHz, DMSO-) is shown. d 6) δ (ppm) 132.35,131.48, 131.03, 130.04, 129.81, 128.59, 128.51, 128.49, 128.15, 127.85,124.03, 123.66, 121.28. Figure 11 The HPLC chromatogram is shown. Figure 12 The HRMS (ESI) m / z calcd for C is shown. 42 H 28 N + (M+H) + 546.21770, found 546.21971. Weigh 5 mg of the guest molecule (V) from step S1 and place it in a clean, dry container. Measure 1 mL of the main (I) solution from Example 1 and dissolve the sample weighed in step S2 at a doping ratio of 5% by mass. Disperse the solution uniformly by ultrasonication. After the solvent has completely evaporated, a thin film material with photostimulation response is obtained.

[0063] II. Verification of Photoactivated Phosphorescence Performance Example 6: The thin film material in Example 2 exhibits blue fluorescence emission under ultraviolet light irradiation, such as... Figure 18 As shown in (II); after 10 seconds of ultraviolet light irradiation, it exhibits green phosphorescence, as... Figure 18 As shown in (II). The photoactivated phosphorescence spectrum of the thin film material in Example 2 is as follows. Figure 19 As shown in (II), phosphorescence emission is enhanced after continuous ultraviolet lamp irradiation. The phosphorescence decay curve of the thin film material in Example 2 after photoactivation is shown below. Figure 20 As shown in (II).

[0064] Example 7: The thin film material in Example 3 exhibits blue fluorescence emission under ultraviolet light irradiation, such as... Figure 18 As shown in (III); when the UV lamp is turned off, it exhibits a short period of phosphorescence emission; after continuous UV irradiation, the film exhibits a bright and persistent yellow-green phosphorescence, as shown in (III). Figure 18 As shown in (III). The phosphorescence spectra of the thin film material in Example 3 before and after photoactivation are as follows. Figure 17 As shown, phosphorescence emission is enhanced after continuous ultraviolet light irradiation. The phosphorescence decay curve of the thin film material in Example 3 after photoactivation is shown below. Figure 20 As shown in (III).

[0065] Example 8: The thin film material in Example 4 exhibits blue fluorescence emission under ultraviolet light irradiation, such as... Figure 18 As shown in (IV); after 10 seconds of UV irradiation, the film exhibits yellow-green phosphorescence emission, as... Figure 18 As shown in (IV). The photoactivated phosphorescence spectrum of the thin film material in Example 4 is as follows. Figure 19 As shown in (IV), phosphorescence emission is enhanced after continuous ultraviolet lamp irradiation. The phosphorescence decay curve of the thin film material in Example 4 after photoactivation is shown below. Figure 20 As shown in (IV).

[0066] Example 9: The thin film material in Example 5 exhibits blue fluorescence emission under ultraviolet light irradiation, such as... Figure 18 (V) indicates that after 10 seconds of ultraviolet light irradiation, it exhibits orange phosphorescence, as shown. Figure 18 As shown in (V). The photoactivated phosphorescence spectrum of the thin film material in Example 5 is as follows. Figure 19 As shown in (V), phosphorescence emission is enhanced after continuous ultraviolet lamp irradiation. The phosphorescence decay curve of the thin film material in Example 5 after photoactivation is shown in Figure 5. Figure 20 As shown in (V).

[0067] III. Performance Verification of Photochromic Materials Example 10: The thin film material in Example 2, before being irradiated by ultraviolet light, appears colorless and transparent, its color varying from colorless to blue-green, such as... Figure 21 As shown in (II). The time-dependent absorption spectrum of the thin film material in Example 2 under ultraviolet light irradiation is shown in 22A, with a new absorption peak appearing at 640 nm. After the ultraviolet light irradiation was turned off, and the film was placed in a natural environment for a period of time, its time-dependent absorption spectrum is shown in 22B, with the absorption peak intensity at 640 nm gradually decreasing, and the film color returning to its original state. The photochromic reversible cycling of the thin film material in Example 2 is as follows: Figure 23 As shown, its cycle count can reach more than 20 times.

[0068] Example 11: The thin film material in Example 3, before being irradiated by ultraviolet light, appears colorless and transparent, its color varying from colorless to blue-green, such as... Figure 21 As shown in (III). The time-dependent absorption spectrum of the thin film material in Example 3 under ultraviolet light irradiation is shown in 24A, with a new absorption peak appearing at 630 nm. After the ultraviolet light irradiation was turned off, and the film was placed in a natural environment for a period of time, its time-dependent absorption spectrum is shown in 24B, with the absorption peak intensity at 630 nm gradually decreasing, and the film color returning to its original state. The photochromic reversible cycling of the thin film material in Example 3 is as follows: Figure 25 As shown, its cycle count can reach more than 20 times.

[0069] Example 12: The thin film material in Example 4, before being irradiated by ultraviolet light, appears colorless and transparent, its color varying from colorless to blue-green, such as... Figure 21As shown in (IV). The time-dependent absorption spectrum of the thin film material in Example 4 under UV irradiation is shown in 26A, with a new absorption peak appearing at 624 nm. After the UV irradiation was turned off and the film was placed in a natural environment for a period of time, its time-dependent absorption spectrum is shown in 26B, with the absorption peak intensity at 624 nm gradually decreasing, and the film color returning to its original state. The photochromic reversible cycling of the thin film material in Example 4 is as follows: Figure 27 As shown, its cycle count can reach more than 20 times.

[0070] IV. Applications of Photoresponsive Materials Example 13: As Figure 29 The eyeglasses device shown involves cutting and placing the thin film material from Embodiment 3 or Embodiment 4 into the eyeglass frame. For example... Figure 29 As shown, eyeglass lenses that are not exposed to sunlight are colorless and transparent. After being exposed to direct sunlight for a period of time, the thin film material turns blue-green and transparent, effectively blocking ultraviolet rays and protecting the eyes.

[0071] Example 14: Weigh 50 mg of guest molecule (III) and place it in a clean, dry container. Measure 10 mL of the host (I) solution and dissolve the guest molecule (III) at a doping ratio of 5% by mass. Disperse the solution uniformly by ultrasonication until the sample is completely dissolved. Allow the solvent to evaporate slowly to obtain a printing solution with high viscosity. Figure 30 The diagram illustrates screen printing. After the device is fixed in place, the viscous solution obtained in step S1 is poured into the template, and the pattern is printed using a pressing method. The printed pattern is then placed in a dry and clean environment to air dry naturally, thus obtaining the hidden screen-printed pattern. Figure 30 As shown, the printed pattern is colorless, transparent, and invisible. After being exposed to ultraviolet light, a clear blue-green pattern appears. After being placed in a natural environment for 20 minutes, the pattern fades and becomes invisible again. This cyclically reversible fatigue resistance can be applied to information encryption and decryption.

[0072] Example 15: As Figure 31 As shown, when the thin film material from Example 3 was placed on the school emblem and irradiated with ultraviolet light, it turned blue-green. The characters on the school emblem were still clearly visible through the film, demonstrating the high transparency of the thin film material. Figure 32 The pattern imprinting device shown in Example 3 places the thin film material under a mask and irradiates it with ultraviolet light to imprint pattern information. The pattern information in the thin film is then observed. Figure 32 As shown, the area illuminated by the ultraviolet lamp displays a clearly visible blue-green "flower" pattern. Under natural conditions, the green "flower" pattern gradually erases and disappears, and this process can be repeated multiple times. This demonstrates how the reversible photochromic property can be applied to erasable and rewriteable information.

[0073] Example 16: As Figure 33 The 3D printing apparatus shown was used to weigh 100 mg of guest molecule (III) and 40 mL of resin solution into a clean, dry container. After mixing thoroughly, the mixture was placed in the Shape 1 HD 3D printer, and photopolymerization and photocuring were performed using the "Standard V1" software in ShapeWare to obtain the printed sample. The 3D printed sample is white in natural conditions. Under ultraviolet light, it exhibits blue fluorescence emission; after 1 minute of ultraviolet light irradiation, it exhibits bright and persistent yellow-green phosphorescence, such as... Figure 33 As shown.

[0074] In summary, this invention utilizes four N-type small molecules doped into a PMMA film to achieve photochromic and room-temperature phosphorescent photostimulation-responsive thin film materials through π-conjugation modulation. The triarylamine derivative serves as the functional guest, and π-conjugation is regulated by controlling the ratio of naphthalene to phenanthrene units. Simultaneously, the PMMA matrix provides a uniform and rigid dispersion environment for the guest molecules, effectively inhibiting molecular aggregation and quenching. This results in a thin film with excellent transparency, flexibility, and fatigue resistance, allowing for repeated recycling hundreds of times.

[0075] The above description is only a preferred embodiment of the present invention. For those skilled in the art, there will be changes in the specific implementation and application scope based on the ideas of the present invention. The content of this specification should not be construed as a limitation of the present invention.

Claims

1. A thin film material exhibiting photochromic properties and / or room-temperature phosphorescence, characterized in that, It includes a polymethyl methacrylate (PMMA) host (I) and a guest doped in the PMMA host, the guest having a structure shown in the following formula: ； Wherein, R1, R2, and R3 are independently naphthyl or phenanthryl; R1, R2, and R3 may be the same or different; preferably, at least one of R1, R2, and R3 is different.

2. The thin film material with photochromic and / or room temperature phosphorescence according to claim 1, characterized in that, The object structures are shown as in (II), (III), (IV), and (V); preferably, as shown in (III) and (IV). 。 3. The thin film material with photochromic properties and / or room temperature phosphorescence according to claim 1, characterized in that, (II), (III), (IV), and (V) are prepared in the following manner; 。 4. The thin film material with photochromic and / or room temperature phosphorescence according to claim 1, characterized in that, The doping amount of the object is 1-10%; preferably 5%.

5. A method for preparing a thin film material with photochromic properties and / or room temperature phosphorescence as described in any one of claims 1-4, characterized in that, Includes the following steps: S1. Weigh the polymethyl methacrylate (PMMA) matrix and place it in a clean, dry container. Add tetrahydrofuran solvent until completely dissolved to prepare a PMMA matrix solution; preferably, the PMMA matrix solution has a concentration of 100 mg / mL. S2. According to the doping ratio, measure the main PMMA solution from step S1 and dissolve the guest sample weighed in step S2. Disperse the sample evenly by ultrasonication until the sample is completely dissolved. After the solvent has completely evaporated, a thin film material with photostimulation response is obtained.

6. The application of a thin film material having photochromic properties and / or room temperature phosphorescence as described in any one of claims 1-4.

7. The application according to claim 6, characterized in that, It is applied in anti-counterfeiting, information encryption and decryption, erasable materials, optical photochromic sunglasses and 3D printing.

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