A halogenated benzene derivative and its preparation method, a light-activated thin film material and its preparation method and application

Abstract

The present patent application provides a halogen benzene derivative and its preparation method and application. The halogen benzene derivative has a structural formula as shown in formula (I), X is a halogen atom (F, Cl, Br), and R is an electron donor group. The present patent application uses a halogen benzene group as an acceptor structure to connect different donor groups R, and synthesizes a guest material through a Suzuki reaction, while the host material is polymethyl methacrylate (PMMA). A light-activated light-stimulation-responsive film material can be obtained by a host-guest doping method, which exhibits different luminous intensities under different illumination times of a 365nm ultraviolet lamp. The light-activated characteristics of the film having different luminous intensities under different illumination times can be applied to display, information encryption, anti-counterfeiting and other aspects.

Description

Technical Field

[0001] The present patent application relates to the field of organic compounds, and more specifically, to a halogenated benzene derivative and a preparation method thereof, a light-activated thin film material and a preparation method and application thereof. Background Art

[0002] The dynamic response of polymer-based room temperature phosphorescent (RTP) materials to external stimuli such as excitation wavelength, temperature, and surrounding environment has always been a research hotspot. Among them, amorphous organic room temperature phosphorescent polymers have been widely studied due to their advantages such as good flexibility, repeatability, and simple processing.

[0003] However, the synthesis of polymer-based room temperature phosphorescent materials in the prior art is relatively complex and the yield is not high; in addition, due to the singlet-triplet energy level difference (ΔE ST ) is large, and its RTP performance is poor, and it is necessary to further search for polymer-based room temperature phosphorescent materials with excellent performance.

[0004] Patent application content

[0005] In order to overcome one of the problems existing in the above-mentioned prior art, the primary purpose of this patent application is to provide a halobenzene derivative. The halobenzene derivative uses a halobenzene group as an acceptor group and a donor group as R, and synthesizes a class of guest compounds through Suzuki reaction.

[0006] Another object of the present patent application is to provide a method for preparing the above-mentioned halobenzene derivatives.

[0007] Another object of the present patent application is to provide a light-activated thin film material.

[0008] Another object of this patent application is to provide a method for preparing the above-mentioned light-activated thin film material

[0009] Another purpose of the present patent application is to provide the application of the above-mentioned light-activated thin film material in the field of anti-counterfeiting and information encryption and decryption.

[0010] The halogenated benzene derivatives in this patent application are doped as guest molecules in the host PMMA to obtain a thin film material with a photo-activated phenomenon. This type of thin film material shows different RTP intensities under different irradiation times of a 365nm ultraviolet lamp. Based on this property of photo-activation, it can be applied to fields such as anti-counterfeiting and information encryption.

[0011] The above-mentioned purpose of this patent application is achieved through the following technical solutions:

[0012] A halogenated benzene derivative, characterized in that the structural formula of the halogenated benzene derivative has a structure as shown in formula (I):

[0013]

[0014] Wherein, R is an electron donor group, and R is selected from any one of the following groups:

[0015]

[0016] Preferably, the molecular structure of the halogenated benzene derivative is one of the following structural formulas (wherein X=F, Cl, Br, I):

[0017] The present patent application also provides a method for preparing the above-mentioned halobenzene derivative, characterized in that it comprises the following steps: under the protection of an inert gas, 4-halobenzene boronic acid, R-Br, tetrakistriphenylphosphine palladium, potassium carbonate aqueous solution and a mixed solvent of tetrahydrofuran are reacted together, and after reacting at 50 to 70°C for 5 to 10 hours, a halobenzene derivative having a structure shown in formula (I) is obtained. The present patent application also provides a photoactivated thin film material, comprising a host material and a mutually doped guest material, wherein the host material is PMMA, and the guest material is the above-mentioned halobenzene derivative. Preferably, the doping mass fraction of the guest material in the host material is 3%. The present patent application also provides a method for preparing the above-mentioned light-activated thin film material, comprising the following steps: S1. Weigh the main material PMMA and put it into a clean and dry container, add the main solvent until it is completely dissolved to prepare the main PMMA solution; S2. Weigh the guest materials separately and put them into a clean and dry container to prepare the guest sample; S3. With the mass fraction of the guest material doped in the main material being 3%, measure the main PMMA solution in step S1 and the guest sample in step 2, dissolve the guest sample in the main PMMA solution to make it completely dissolved, and then evenly apply it on a glass slide, and after the solvent evaporates completely, obtain the light-activated thin film material. Preferably, the main solvent in step S1 is tetrahydrofuran. Preferably, in step S3, the guest sample is dissolved in the PMMA main solution, and the guest sample is completely dissolved by ultrasound. The present patent application also provides the application of the above-mentioned light-activated thin film material in the field of information encryption and decryption. The present patent application also provides the application of the above-mentioned light-activated thin film material in the field of anti-counterfeiting. Compared with the prior art, the beneficial effects of the present patent application are as follows: the present patent application uses the halogen benzene group as the acceptor group, connects different electron acceptor groups R, and synthesizes the halogen benzene derivatives through the Suzuki reaction. The DA structure is formed between the donor and the acceptor of the halogen benzene derivatives, which can effectively reduce the singlet-triplet energy level difference (ΔE ST), thereby promoting self-selected orbital coupling and enhancing RTP performance. The synthesis of halobenzene derivatives by Suzuki reaction has simple synthesis steps and high yields, and the main material PMMA is an easily available and cheap industrially produced polymer with the advantages of high mechanical strength, strong tensile and impact resistance.

[0018] The light-activated thin film material prepared in the present patent application exhibits different RTP emission intensities after being irradiated with ultraviolet light for different times, and can be restored to its original state after being placed under oxygenated conditions for a period of time. This is a fast response process, so this feature can be used in the fields of information encryption and decryption, anti-counterfeiting, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 The halobenzene derivative A1 prepared in Example 1 1 HMNR diagram;

[0020] Figure 2 is the mass spectrum of the halobenzene derivative A1 prepared in Example 1;

[0021] Figure 3 The halobenzene derivative A2 prepared in Example 2 1 HMNR diagram;

[0022] Figure 4 is the mass spectrum of the halobenzene derivative A2 prepared in Example 2;

[0023] Figure 5 The halobenzene derivative A3 prepared in Example 3 1 HMNR diagram;

[0024] Figure 6 is the mass spectrum of the halobenzene derivative A3 prepared in Example 3;

[0025] Figure 7 The RTP delayed emission spectrum of the light-activated thin film material L prepared in Example 5;

[0026] Figure 8 Schematic diagram of the activated film material L being quenched after being exposed to air for 2 minutes

[0027] Fig. 9 The RTP delayed emission spectrum of the light-activated thin film material M prepared in Example 6;

[0028] Fig.10 Schematic diagram of the activated film material M being quenched again after being exposed to air for 2 minutes;

[0029] Fig.11 The RTP delayed emission spectrum of the light-activated thin film material N prepared in Example 7;

[0030] Fig.12 Schematic diagram of the activated thin film material N being quenched again after being exposed to air for 2 minutes;

[0031] Fig.13 This is a schematic diagram of the principle that the light-activated thin film material in this patent application can improve the luminescence performance of phosphorescence. DETAILED DESCRIPTION

[0032] The embodiments of the present patent application will be described in detail below in conjunction with the examples, but those skilled in the art will appreciate that the following examples are only used to illustrate the present patent application and should not be considered to limit the scope of the present patent application. If the specific conditions are not specified in the examples, they are carried out according to the normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0033] It should be noted that:

[0034] In this patent application, unless otherwise specified, all implementation methods and preferred implementation methods mentioned herein can be combined with each other to form a new technical solution.

[0035] In the present patent application, unless otherwise specified, percentage (%) or part refers to the weight percentage or weight part relative to the composition.

[0036] In this patent application, unless otherwise specified, the components or preferred components involved can be combined with each other to form a new technical solution.

[0037] In this patent application, unless otherwise specified, the numerical range "a-b" represents an abbreviation of any real number combination between a and b, where a and b are real numbers. For example, the numerical range "1-5" means that all real numbers between "1-5" are listed in this document, and "1-5" is just an abbreviation of these numerical combinations.

[0038] The “range” disclosed in this patent application is in the form of a lower limit and an upper limit, which can be one or more lower limits, and one or more upper limits, respectively.

[0039] In this patent application, unless otherwise specified, each reaction or operation step can be carried out in sequence or in accordance with the sequence. Preferably, the reaction method herein is carried out in sequence.

[0040] Unless otherwise specified, the professional and scientific terms used herein are the same as those familiar to those skilled in the art. In addition, any method or material similar or equivalent to the described content may also be applied to this patent application.

[0041] The present patent application provides a halogenated benzene derivative, characterized in that the structural formula of the halogenated benzene derivative has a structure as shown in formula (I):

[0042]

[0043] Wherein, R is an electron donor group, and R is selected from any one of the following groups:

[0044]

[0045] In some preferred embodiments, the molecular structure of the halobenzene derivative is one of the following structural formulas (wherein X=F, Cl, Br, I):

[0046]

[0047]

[0048] The halogenated benzene derivatives provided in the present patent application use the halogenated benzene group as the acceptor group, connect different electron acceptor groups R, and synthesize the halogenated benzene derivatives through the Suzuki reaction. The DA structure is formed between the donor and the acceptor of the halogenated benzene derivatives, which can effectively reduce the singlet-triplet energy level difference (ΔE ST ), thereby promoting self-selected orbital coupling and enhancing RTP performance.

[0049] This patent application also provides a method for preparing the above-mentioned halobenzene derivatives, which is characterized by comprising the following steps:

[0050] Under the protection of inert gas, 4-halobenzene boronic acid, R-Br, tetrakistriphenylphosphine palladium, potassium carbonate aqueous solution and tetrahydrofuran mixed solvent are reacted together at 50-70° C. for 5-10 hours to obtain a halobenzene derivative having a structure shown in formula (I).

[0051] The preparation method of the above-mentioned halobenzene derivatives in this patent application synthesizes the halobenzene derivatives through Suzuki reaction, and the synthesis steps are simple and the yield is high. The main material PMMA is an easily available and cheap industrially produced polymer with the advantages of high mechanical strength, strong tensile and impact resistance, etc.

[0052] In some more preferred embodiments, the method for preparing the halobenzene derivative in the present patent application comprises the following steps:

[0053] Under nitrogen protection, 4-halobenzeneboric acid, R-Br, tetrakistriphenylphosphine palladium, potassium carbonate aqueous solution and tetrahydrofuran as solvent in a volume ratio of 1:5 were reacted at 70° C. for 8 h to obtain a product having a structure shown in formula (I).

[0054] The present patent application also provides a light-activated thin film material, comprising a host material and mutually doped guest materials, wherein the host material is PMMA, and the guest material is the above-mentioned halogenated benzene derivative.

[0055] The light-activated film material prepared in this patent application exhibits different RTP emission intensities after being irradiated with ultraviolet light for different times, and can be restored to its original state after being placed under oxygenated conditions for a period of time. This is a fast response process. Therefore, this feature can be used in the fields of information encryption and decryption, anti-counterfeiting, etc.

[0056] In some preferred embodiments, the doping mass fraction of the guest material in the host material is 3%.

[0057] This patent application also provides a method for preparing the above-mentioned light-activated thin film material, comprising the following steps:

[0058] S1. Weigh the main material PMMA into a clean and dry container, add the main solvent until it is completely dissolved to configure the main PMMA solution;

[0059] S2. Weigh the guest materials separately and put them into clean and dry containers to prepare guest samples;

[0060] S3. With the mass fraction of the guest material doped in the host material being 3%, measure the host PMMA solution in step S1 and the guest sample in step 2, dissolve the guest sample in the host PMMA solution to make it completely dissolved, and then evenly apply it on a glass slide. After the solvent evaporates completely, the photoactivated thin film material is obtained.

[0061] The halogenated benzene derivative light-activated thin film material prepared in this patent application is based on a thin film of small molecule-doped polymers and has light-activated behavior characteristics, which is the special feature of this light-stimulus-responsive thin film material.

[0062] In some preferred embodiments, the main solvent in step S1 is tetrahydrofuran.

[0063] In some preferred embodiments, in step S3, the guest sample is dissolved in the PMMA main solution, and ultrasound is used to completely dissolve the guest sample.

[0064] This patent application also provides the application of the above-mentioned light-activated thin film material in the field of information encryption and decryption.

[0065] This patent application also provides the application of the above-mentioned light-activated thin film material in the field of anti-counterfeiting.

[0066] The applicant of the present patent has obtained a polymer film with photoactivation properties by embedding the above-mentioned halobenzene derivatives into a rigid PMMA matrix. The reason for the photoactivation may be that after the molecules are exposed to light, the interaction between the molecules is strengthened and the angle between the molecules is changed, so that the movement of the molecules is restricted, thereby generating afterglow; or because the light changes the environment around the molecules. For example, in the PMMA doped film, the light consumes triplet oxygen, ensuring that the triplet excitons of the molecules are not quenched, thereby generating afterglow. In addition, based on the photoactivation characteristics of the film, a variety of encryption modes are designed to demonstrate the potential application of these halobenzene derivatives in multi-level anti-counterfeiting and information encryption technologies, with ultra-long life, adjustable persistent luminescence and ultraviolet radiation responsiveness.

[0067] The photo-activated film material in this patent application, under the irradiation of ultraviolet light, the main material PMMA polymer wraps the small molecule (i.e. the guest material, halogenated benzene derivative), effectively hardening the phosphor and its environment. Among them, mainly the irradiation of ultraviolet light can consume the triplet oxygen in the film and promote its conversion into singlet oxygen, thereby avoiding the quenching of the triplet excitons of the small molecule, thereby improving the luminescence performance of the phosphorescence.

[0068] The light stimulus response behavior in this patent application is due to the host-guest doping of the host material (PMMA) and the guest material compound of formula (I), and then the doped film is formed by spin coating. When the doped film is not continuously irradiated by a 365nm ultraviolet lamp, A1, A2 and A3 have no afterglow, but after continuous irradiation by a 365nm ultraviolet lamp, the film gradually shows green afterglow, and the RTP emission intensity reaches a saturation value after continuous irradiation for 12 seconds. The phenomenon displayed by the film before and after irradiation by a 365nm ultraviolet lamp reflects the characteristics of light activation.

[0069] In the preparation method of the halogenated benzene derivatives of the present patent application, the product having the structure shown in formula (I) obtained by the synthesis in the step is a crude product of the target compound, which can be purified by an existing conventional purification method to improve the purity of the compound shown in formula (I), specifically, it can be purified by recrystallization or silica gel column chromatography: when recrystallization is used for purification, the solvent used for recrystallization is a combination of a good solvent and a poor solvent, preferably a combination of dichloromethane and n-hexane; when column chromatography is used for purification, specifically, the target compound obtained in the step is subjected to silica gel column chromatography, eluted with an eluent composed of petroleum ether and dichloromethane in a volume ratio of (1 to 10): 1 (preferably eluted with an eluent composed of petroleum ether and dichloromethane in a volume ratio of 6: 1), and the solvent is removed by rotary evaporation to obtain the purified target compound.

[0070] The preparation methods of the p-halobenzene derivative compounds of formula (I), with compounds A1, A2 and A3 as representative examples, are described in detail below.

[0071] Example 1

[0072] This embodiment provides a halobenzene derivative, the structural formula of which is shown in A1:

[0073]

[0074] The reaction equation and preparation method of the compound are as follows:

[0075]

[0076] Weigh 4-boric acid triphenylamine (1.15g, 4mmol), 4-bromo-4-fluorobenzene (0.36g, 2mmol), tetrakistriphenylphosphine palladium (0.11g, 0.1mmol), and potassium carbonate (1.1g, 8mmol) into a 250ml double-necked flask, evacuate and fill with nitrogen, add 20ml tetrahydrofuran solvent and 4ml water, and stir and react for 8h at a reaction temperature of 70°C under nitrogen protection. After the reaction is completed, cool it to room temperature, extract it with dichloromethane, and separate it by silica gel column chromatography (eluent is petroleum ether: dichloromethane = 6:1).

[0077] Example 2

[0078] This embodiment provides a halobenzene derivative, the structural formula of which is shown in A2:

[0079]

[0080] The reaction equation and preparation method of the compound are as follows:

[0081]

[0082] Weigh 4-bromotriphenylamine (648 mg, 2 mmol), p-chlorophenylboric acid (624 mg, 4 mmol), tetrakistriphenylphosphine palladium (0.11 g, 0.1 mmol), and potassium carbonate (1.1 g, 8 mmol) into a 250 ml double-necked flask, evacuate and fill with nitrogen, add 20 ml of tetrahydrofuran solvent and 4 ml of water, and stir and react for 8 hours at a reaction temperature of 70°C under nitrogen protection. After the reaction is completed, cool it to room temperature, extract it with dichloromethane, and separate it by silica gel column chromatography (eluent is petroleum ether: dichloromethane = 5:1).

[0083] Example 3

[0084] This embodiment provides a halobenzene derivative, the structural formula of which is shown in A3:

[0085]

[0086] The reaction equation and preparation method of the compound are as follows:

[0087]

[0088] Weigh 4-boric acid triphenylamine (1.15g, 4mmol), p-bromoiodobenzene (0.56g, 2mmol), tetrakistriphenylphosphine palladium (0.11g, 0.1mmol), potassium carbonate (1.1g, 8mmol) into a 250ml double-necked flask, evacuate and fill with nitrogen, add 20ml tetrahydrofuran solvent and 4ml water, and stir the reaction at 70°C for 8h under nitrogen protection. After the reaction is completed, cool it to room temperature, extract it with dichloromethane, and separate it with silica gel column chromatography (eluent is petroleum ether: dichloromethane = 6:1).

[0089] Next, the photoactive thin film materials L, M and N are prepared by using the halogenated benzene derivatives A1, A2 and A3 as guest materials, and the preparation methods thereof are described in detail.

[0090] Example 4

[0091] Solution preparation of the main molecule polymethyl methacrylate (PMMA):

[0092] S1. Weigh 10g of the main material PMMA and place it in a dry and clean 250mL round-bottom flask, add 100mL of tetrahydrofuran solvent, block the flask mouth with a condenser, stir at room temperature, and after the sample is completely dissolved, a colorless and transparent solution with a concentration of 100mg / mL is obtained.

[0093] Example 5

[0094] The preparation method of the light-activated thin film material L using the halogenated benzene derivative A1 as the guest material is as follows:

[0095] S2. Weigh 3 mg of guest molecule A1 into a centrifuge tube.

[0096] S3. Take 1 ml of the main solution in Example 4 with a mass fraction of 3%, put the solution into the centrifuge tube in step S2, mix it evenly by ultrasonication, and then evenly drop the mixture onto the quartz plate. After the solvent evaporates completely, a thin film material L with light activation phenomenon is obtained.

[0097] Example 6

[0098] The preparation method of the light-activated thin film material M using the halogenated benzene derivative A2 as the guest material is as follows:

[0099] S2. Weigh 3 mg of guest molecule A2 into a centrifuge tube.

[0100] S3. Take 1 ml of the main solution in Example 4 with a mass fraction of 3%, put the solution into the centrifuge tube in step S2, mix it evenly by ultrasonication, and then evenly drop the mixture onto a quartz plate. After the solvent evaporates completely, a thin film material M with a photoactivated phenomenon is obtained.

[0101] Example 7

[0102] The preparation method of the photoactivated thin film material N using the halogenated benzene derivative A3 as the guest material is as follows:

[0103] S2. Weigh 3 mg of guest molecule A3 into a centrifuge tube.

[0104] S3. Take 1 ml of the main solution in Example 4 with a mass fraction of 3%, put the solution into the centrifuge tube in step S2, mix it evenly by ultrasonication, and then evenly drop the mixture onto the quartz plate. After the solvent evaporates completely, a thin film material N with photoactivation phenomenon is obtained.

[0105] Characterization and performance testing

[0106] The compounds or materials prepared in Examples 1, 2, 3, 5, 6 and 7 were characterized and / or tested for performance. The results are as follows: Figures 1 to 12 shown.

[0107] The product prepared in Example 1 was subjected to nuclear magnetic resonance detection. Specifically, a Bruker 400 MHz superconducting nuclear magnetic resonance instrument was used, and the solvent was deuterated chloroform. The hydrogen spectrum obtained by the measurement was as follows: Figure 1 As shown, the characteristic wave number (ppm) is 1 H NMR (400MHz, Chloroform-d) δ7.53–7.48 (m, 1H), 7.43–7.39 (m, 1H), 7.29–7.24 (m, 2H), 7.14–7.00 (m, 5H). It can be seen that the molecular hydrogen spectrum peaks can correspond to the target product one by one, and the quantity is reasonable. This shows that Example 1 prepared the compound shown in the halogenated benzene biological A1, and the compound has a single structure and high purity;

[0108] Mass spectrometry detection: The halobenzene derivative A1 obtained in Example 1 was dissolved in dichloromethane to prepare a solution with a concentration of 1 mg / mL. A liquid chromatography-tandem triple quadrupole mass spectrometer was used to perform mass spectrometry test. The test results are shown in FIG. Figure 2 As shown, from Figure 2 It can be concluded that the relative molecular mass of the halobenzene derivative A1 is 340.02. If one H is subtracted, it is the same as the relative molecular mass of the synthesized compound A1, which further proves that the compound prepared in Example 1 is the compound shown by the halobenzene derivative A1, and the compound has a single structure and high purity.

[0109] The product prepared in Example 2 was subjected to nuclear magnetic resonance detection. The structural formula was determined using a Bruker 400 MHz superconducting nuclear magnetic resonance instrument with deuterated chloroform as the solvent. The hydrogen spectrum obtained by the determination was as follows: Figure 3 As shown, the characteristic wave number (ppm) is 1 H NMR (400MHz, Chloroform-d) δ7.55–7.35 (m, 6H), 7.27 (td, J=7.3, 1.4Hz, 4H), 7.17–7.08 (m, 6H), 7.07–7.01 (m, 2H). It can be seen that the molecular hydrogen spectrum peaks can correspond to the target product one by one, and the quantity is reasonable. This shows that Example 2 prepared the compound shown in halobenzene biomolecule A2, and the compound has a single structure and high purity;

[0110] Mass spectrometry detection: The halobenzene derivative A2 obtained in Example 2 was dissolved in dichloromethane to prepare a solution with a concentration of 1 mg / mL. A liquid chromatography-tandem triple quadrupole mass spectrometer was used for mass spectrometry testing. The test results are as follows: Figure 4 As shown in the figure, it can be concluded that the relative molecular mass of the halobenzene derivative A2 is 355.98. If one H is subtracted, it is the same as the relative molecular mass of the synthesized compound A2, which further proves that the compound prepared in Example 2 is the compound shown as the halobenzene derivative A2, and the compound has a single structure and high purity.

[0111] The product prepared in Example 3 was subjected to nuclear magnetic resonance detection. The structural formula was determined using a Bruker 400 MHz superconducting nuclear magnetic resonance instrument and deuterated dimethyl sulfoxide as solvent. The hydrogen spectrum obtained by the determination was as follows: Figure 5 As shown, the characteristic wave number (ppm) is 1 HNMR (400MHz, Chloroform-d) δ7.55–7.49 (m, 2H), 7.45–7.38 (m, 4H), 7.30–7.25 (m, 4H), 7.16–7.08 (m, 6H), 7.04 (td, J=7.3, 1.3Hz, 2H). It can be seen that the molecular hydrogen spectrum peaks can correspond to the target product one by one, and the quantity is reasonable. This shows that Example 3 prepared the compound shown in halobenzene biomolecule A3, and the compound has a single structure and high purity;

[0112] Mass spectrometry detection: The halobenzene derivative A3 obtained in Example 3 was dissolved in dichloromethane to prepare a solution with a concentration of 1 mg / mL. A liquid chromatography-tandem triple quadrupole mass spectrometer was used to perform mass spectrometry test. The test results are as follows: Figure 6As shown in the figure, it can be concluded that the relative molecular mass of the halobenzene derivative A3 is 401.93. If one H is subtracted, it is the same as the relative molecular mass of the synthesized compound A3, which further proves that the compound prepared in Example 3 is the compound shown as the halobenzene derivative A3, and the compound has a single structure and high purity.

[0113] Figure 7 The RTP delayed emission spectrum of the light activated thin film material L prepared in Example 5 is shown in FIG. Figure 7 It can be seen that when there is no 365nm UV light irradiation (that is, when the UV light irradiation time is 0S in the figure), the light-activated film material L formed by doping the halogenated benzene derivative A1 with PMMA has almost no afterglow. As the UV light irradiation time increases from 4 seconds to 8 seconds and finally to 12 seconds, green afterglow begins to appear, and the RTP intensity of the light-activated film material L gradually increases and reaches saturation at 12 seconds. The activated film material L is exposed to air for 2 minutes and then quenched (such as Figure 8 ), and can be reactivated by irradiation with ultraviolet light. Therefore, it is shown that the light-activated film has good stability and reversibility.

[0114] Fig. 9 The RTP delayed emission spectrum of the light activated thin film material M prepared in Example 6 is shown in FIG. Fig. 9 It can be seen that when there is no 365nm UV light irradiation (that is, when the UV light irradiation time is 0S in the figure), the light-activated film material M formed by doping the halogenated benzene derivative A2 with PMMA has no afterglow. As the UV light irradiation time increases from 4 seconds to 8 seconds and finally to 12 seconds, a green afterglow begins to appear, and the RTP intensity of the light-activated film material M gradually increases and reaches saturation at 12 seconds. The activated film material M will be quenched again if it is exposed to air for 2 minutes (such as Fig.10 ), and can be reactivated by irradiation with ultraviolet light. Therefore, it is shown that the light-activated film has good stability and reversibility.

[0115] Fig.11 The RTP delayed emission spectrum of the light activated thin film material N prepared in Example 7 is shown in FIG. Fig.11 It can be seen that when there is no 365nm UV light irradiation (that is, when the UV light irradiation time is 0S in the figure), the light-activated thin film material N formed by doping the halogenated benzene derivative A3 with PMMA has no afterglow. As the UV light irradiation time increases from 4 seconds to 8 seconds and finally to 12 seconds, a green afterglow begins to appear, and the RTP intensity of the light-activated thin film material N gradually increases and reaches saturation at 12 seconds. The activated thin film material N will be quenched again if it is exposed to air for 2 minutes (such as Fig.12 ), and can be reactivated by irradiation with ultraviolet light. Therefore, it is shown that the light-activated film has good stability and reversibility.

[0116] This patent application uses the halogen benzene group as the acceptor group, connects different electron acceptor groups R, and synthesizes the halogen benzene derivatives through the Suzuki reaction. The DA structure is formed between the donor and the acceptor of the halogen benzene derivative, which can effectively reduce the singlet-triplet energy level difference (ΔE ST ), thereby promoting self-selected orbital coupling and enhancing RTP performance. The synthesis of halobenzene derivatives by Suzuki reaction has simple synthesis steps and high yields, and the main material PMMA is an easily available and cheap industrially produced polymer with the advantages of high mechanical strength, strong tensile and impact resistance.

[0117] The light-activated thin film material prepared in the present patent application exhibits different RTP emission intensities after being irradiated with ultraviolet light for different times, and can be restored to its original state after being placed under oxygenated conditions for a period of time. This is a fast response process, so this feature can be used in the fields of information encryption and decryption, anti-counterfeiting, etc.

[0118] Under the irradiation of ultraviolet light, the light-activated film material in this patent application wraps the small molecules (i.e., the guest material, halogenated benzene derivatives) with the host material PMMA polymer, effectively hardening the phosphor and its environment. Among them, the irradiation of ultraviolet light mainly consumes the triplet oxygen in the film and causes it to transform into singlet oxygen, thereby avoiding the quenching of the triplet excitons of the small molecules, thereby improving the luminescence performance of the phosphorescence (schematic diagram as shown in FIG. Fig.13 shown).

[0119] The halogenated benzene derivative light-activated thin film material prepared in this patent application is based on a thin film of small molecule-doped polymers and has light-activated behavior characteristics, which is the special feature of this light-stimulus-responsive thin film material.

[0120] This patent application uses the prepared halobenzene derivative as the guest material, and the host material is polymethyl methacrylate (PMMA). Through the host-guest doping method, a light-activated light stimulus response film material can be obtained, which exhibits different luminescence intensities under different irradiation times of a 365nm ultraviolet lamp. The film has different luminescence intensities under different illumination times and can be used in display, information encryption, anti-counterfeiting and other aspects.

[0121] The light stimulus responsive thin film material prepared in the present patent application, after being activated by ultraviolet light, exhibits different RTP intensities and long afterglow depending on the irradiation time, and can be restored to its original state after being placed under oxygen for a period of time. This is a fast response process, so this feature can be used in the fields of information encryption and decryption, anti-counterfeiting, etc.

[0122] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "illustrative embodiments", "examples", "specific examples", or "some examples" means that the specific features, structures, materials or characteristics described in conjunction with the embodiments or examples are included in at least one embodiment or example of this patent application. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner.

[0123] Although several embodiments of the present patent application have been shown and described, those skilled in the art will appreciate that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present patent application, and the scope of the present patent application is defined by the claims and their equivalents.

Claims

1. A method for preparing a light-activated thin film material, the light-activated thin film material comprising a host material and a mutually doped guest material, wherein the host material is polymethyl methacrylate, the doping mass fraction of the guest material in the host material is 3%, and the guest material is a halogenated benzene derivative and has one of the following structural formulas: It is characterized in that The following steps are involved: S1. Weigh the main material polymethyl methacrylate into a clean and dry container, add the main solvent until it is completely dissolved, to configure the main polymethyl methacrylate solution; S2. Weigh the guest materials separately and put them into clean and dry containers to prepare guest samples; S3. With the mass fraction of the guest material doped in the host material being 3%, measure the host polymethyl methacrylate solution in step S1 and the guest sample in step 2, dissolve the guest sample in the host polymethyl methacrylate solution to make it completely dissolved, and then evenly apply it on a glass slide. After the solvent evaporates completely, the light-activated thin film material is obtained.

2. The method for preparing the light-activated thin film material according to claim 1, characterized in that: The main solvent in step S1 is tetrahydrofuran.

3. The method for preparing the light-activated thin film material according to claim 2, characterized in that: In the step S3, the guest sample is dissolved in the polymethyl methacrylate main solution, and the guest sample is completely dissolved by ultrasound.

4. Application of the photoactive thin film material prepared by the method for preparing the photoactive thin film material according to claim 1 in the field of information encryption and decryption.

5. Application of the light-activated thin film material prepared by the method for preparing the light-activated thin film material according to claim 1 in the field of anti-counterfeiting.

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