Optically activated organic long afterglow material, and preparation method and application thereof

Abstract

The application discloses a kind of photoactivation organic long afterglow material and its preparation method and application.The application of compound of formula (III), formula (IV), formula (V) in photoactivation organic long afterglow material;Structural formula of compound of formula (III), formula (IV), formula (V) is as shown below:formula (III)-(V) as the guest component of photoactivation long afterglow material, the efficiency of generating triplet exciton is higher and its triplet exciton energy transfer to oxygen molecule is stronger, the photoactivation process of long afterglow material prepared by being doped in epoxy polymer is short, and the material after activation can be restored to the state without long afterglow emission by heating annealing, so as to effectively overcome the shortcomings that the current photoactivation long afterglow material needs long activation time and is difficult to restore to unactivated state.

Description

[0001] This application is a divisional application of the application with the application number 2022107990280 and the application name "Light-activated organic long afterglow material and its preparation method and application", the application date of which is July 7, 2022. TECHNICAL FIELD

[0002] The application belongs to the technical field of luminescent materials, and particularly relates to a light-activated organic long afterglow material and its preparation method and application. BACKGROUND

[0003] Long afterglow luminescence refers to the phenomenon that light can be continuously emitted after the excitation source stops exciting. Materials with long afterglow luminescence can effectively eliminate the influence of short-lived background light, greatly improving the signal-to-noise ratio of luminescent signals. Therefore, such materials have broad application prospects in the fields of display lighting, emergency indication, intelligent transportation, biological imaging, data encryption and security anti-counterfeiting. The long afterglow luminescence of organic matter is generally caused by super-long lifetime (τ≥100 ms) phosphorescence emission. However, the triplet exciton is extremely susceptible to temperature and water vapor and oxygen in the environment, and is easily quenched, resulting in that most organic luminescent materials can only produce afterglow emission at low temperature (such as 77K) or in an inert atmosphere, and the application is greatly limited.

[0004] In order to realize organic long afterglow luminescence in room temperature air, researchers have proposed many different strategies, including: 1. Introducing heteroatoms and heavy halogen atoms into molecules to improve the intersystem crossing efficiency; 2. Providing a rigid environment for organic molecules through crystal engineering and making them form special molecular aggregates; 3. Polymerizing organic molecules into polymers; 4. Using host-guest doping to incorporate organic molecules into a solid matrix that can isolate oxygen and limit molecular motion; 5. Preparing carbon dots, etc. Among them, crystal materials do not have flexibility and the reproducibility of the phosphorescent performance of the material is not ideal, and the introduction of heavy halogen atoms often shortens the phosphorescent lifetime. In contrast, polymers have high molecular weight and long molecular chains, which can provide a rigid and dense environment for phosphorescent molecules or chromophores, inhibiting the thermal motion of molecules or groups in the system, thereby facilitating long afterglow luminescence. In addition, polymers also have the advantages of easy processing, flexibility, low preparation cost, etc. Therefore, doping organic molecules into a polymer matrix or synthesizing a polymer containing heteroatom chromophores has become an ideal strategy for obtaining long afterglow materials. However, most of the current polymer materials have low afterglow luminescence efficiency and short lifetime at room temperature, which seriously limits their practical application.

[0005] On the other hand, the polymer material with photo-activated organic long afterglow luminescence characteristics has attracted extensive attention of researchers in recent two years due to its important potential application in anti-counterfeiting, data encryption, optical printing and other fields. However, the material currently generally has problems such as long activation time, i.e. more than 30 minutes of continuous ultraviolet light irradiation is needed for activation, and poor reversibility, i.e. it is difficult to restore to the initial state after activation. At the same time, like most polymer long afterglow materials, the afterglow luminescence performance of the activated material is easily affected by water vapor in the air at room temperature, and the performance decays quickly, the stability is poor, and even the long afterglow luminescence cannot be produced completely within a few hours, which requires re-drying treatment to remove the water vapor absorbed by the polymer. Therefore, it is of important practical significance to develop a polymer material with efficient, stable and fast and reversible photo-activated organic long afterglow properties. SUMMARY

[0006] In order to overcome the problems of long activation time and difficulty in restoring to the unactivated state of the prior art photo-activated long afterglow material, one of the purposes of the present application is to provide the application of the compounds of formula (I)-(V) in photo-activated organic long afterglow materials, the second purpose of the present application is to provide a photo-activated organic long afterglow material, the third purpose of the present application is to provide a preparation method of the photo-activated organic long afterglow material, and the fourth purpose of the present application is to provide the application of the photo-activated organic long afterglow material.

[0007] In order to achieve the above-mentioned purposes, the technical scheme adopted by the present application is:

[0008] The first aspect of the present application provides the application of the compounds of formula (I), formula (II), formula (III), formula (IV) and formula (V) in photo-activated organic long afterglow materials.

[0009] The structural formulae of the compounds of formula (I), formula (II), formula (III), formula (IV) and formula (V) are as follows:

[0010]

[0011] The second aspect of the present application provides a photo-activated organic long afterglow material, which comprises a host component and a guest component doped in the host component, the host component comprises an epoxy polymer, and the guest component comprises at least one of the above-mentioned formula (I), formula (II), formula (III), formula (IV) and formula (V).

[0012] The photo-activated organic long afterglow material of the present application does not have super-long lifetime phosphorescence emission property in the initial state, and after short-time photo-activation, the phosphorescence lifetime is significantly prolonged and the efficiency is greatly improved, so as to produce long lifetime and high efficiency afterglow luminescence, and after heating treatment, it can be restored to the state without super-long lifetime phosphorescence emission, i.e. it has reversible photo-activated organic long afterglow luminescence characteristics.

[0013] During the photoactivation, the energy of the triplet excitons generated by the guest molecules can be effectively transferred to the residual oxygen molecules in the epoxy polymer, so that the residual oxygen molecules are converted into singlet oxygen. The high-activity singlet oxygen then reacts with the epoxy polymer matrix, thereby eliminating the quenching effect of the oxygen molecules in the polymer on the triplet excitons generated by the guest molecules. Since the efficiency of generating triplet excitons by the screened or designed guest molecules is high, the ability of the triplet excitons to transfer energy to the oxygen molecules is also strong. The photoactivation process of the material can be completed in only 90-720s. At the same time, the epoxy polymer has a dense three-dimensional network structure, which can effectively inhibit the movement of the guest molecules and reduce the non-radiative deactivation channels thereof, so that the triplet excitons generated by the guest molecules can return to the ground state through radiation transition, thereby emitting long-lifetime and high-efficiency afterglow.

[0014] In the present application, the photoactivated organic long-afterglow material can be restored to a state without super-long-lifetime phosphorescence emission by heating at 90-120℃ for 6-45min and cooling to room temperature. During the heating, the movement of the molecular chains of the epoxy polymer is intensified, and the oxygen in the air can enter the polymer. After cooling to room temperature, the newly entered oxygen molecules quench the triplet excitons generated by the guest molecules, so that the long-afterglow luminescence cannot be generated.

[0015] Preferably, in the photoactivated organic long-afterglow material, the doping is physical doping.

[0016] Preferably, in the photoactivated organic long-afterglow material, the mole percentage of the guest component is 0.001-5%; further preferably, the mole percentage of the guest component is 0.01-1%; still further preferably, the mole percentage of the guest component is 0.1-0.5%; according to the chemical structure of the doped guest molecules, the color, quantum yield, and lifetime of the afterglow of the organic long-afterglow material can be controlled.

[0017] Preferably, in the photoactivated organic long-afterglow material, the epoxy polymer is polymerized from bisphenol A diglycidyl ether and a curing agent.

[0018] Further preferably, in the photoactivated organic long-afterglow material, the mole ratio of bisphenol A diglycidyl ether, the guest component, and the curing agent is 1:(0.0001-0.05):(0.5-2).

[0019] In some preferred embodiments of the present application, the curing agent is 1,3-propanediamine.

[0020] The third aspect of the present application provides a preparation method of the photoactivated organic long-afterglow material described above, which comprises the following steps:

[0021] The bisphenol A diglycidyl ether, the guest component and the curing agent are mixed and stirred, and then cured to obtain the photoactivated organic long afterglow material.

[0022] Preferably, in the preparation method of the photoactivated organic long afterglow material, the curing temperature is 20-120℃; further preferably, the curing temperature is 40-110℃; still further preferably, the curing temperature is 60-110℃; more preferably, the curing temperature is 80-100℃.

[0023] Preferably, in the preparation method of the photoactivated organic long afterglow material, the curing time is 0.5-48h; further preferably, the curing time is 0.5-24h; still further preferably, the curing time is 0.5-12h; more preferably, the curing time is 1-3h.

[0024] The fourth aspect of the present application provides a preparation method of the compound of formula (III), comprising the following steps:

[0025] The 7H-benzo[c]carbazole and the ethyl 4-halobenzoate are mixed to generate a carbon-nitrogen coupling reaction to obtain the compound of formula (III).

[0026] Preferably, in the preparation method of the compound of formula (III), the halogen group in the ethyl 4-halobenzoate is selected from any one of F, Cl, Br and I; further preferably, the halogen group in the ethyl 4-halobenzoate is Br.

[0027] Preferably, in the preparation method of the compound of formula (III), the solvent used in the reaction process is toluene.

[0028] Preferably, in the preparation method of the compound of formula (III), the basic substance used in the reaction process is potassium phosphate (K3PO4).

[0029] Preferably, in the preparation method of the compound of formula (III), the ligand used in the reaction process is 2-dicyclohexylphosphine-2',6'-diisopropoxy-1,1'-biphenyl (Ruphos).

[0030] Preferably, in the preparation method of the compound of formula (III), the catalyst used in the reaction process is tris(dibenzylideneacetone)dipalladium [Pd2(dba)3].

[0031] Preferably, in the preparation method of the compound of formula (III), the molar ratio of 7H-benzo[c]carbazole to ethyl 4-halobenzoate is (1-3) : 1; more preferably, the molar ratio of 7H-benzo[c]carbazole to ethyl 4-halobenzoate is (1-2) : 1; still more preferably, the molar ratio of 7H-benzo[c]carbazole to ethyl 4-halobenzoate is (1-1.5) : 1; yet more preferably, the molar ratio of 7H-benzo[c]carbazole to ethyl 4-halobenzoate is 1.2:1.

[0032] Preferably, in the preparation method of the compound of formula (III), the reaction is carried out under a protective atmosphere; more preferably, the reaction is carried out under an argon protective atmosphere.

[0033] Preferably, in the preparation method of the compound of formula (III), the reaction temperature is 100-150℃; more preferably, the reaction temperature is 110-140℃; still more preferably, the reaction temperature is 115-130℃; in some preferred embodiments of the present application, the reaction temperature is 120℃.

[0034] Preferably, in the preparation method of the compound of formula (III), the reaction time is 12-36h; more preferably, the reaction time is 18-30h; still more preferably, the reaction time is 22-26h; in some preferred embodiments of the present application, the reaction time is 24h.

[0035] Preferably, in the preparation method of the compound of formula (III), after the reaction is completed, the product is further subjected to separation and purification, reprecipitation, suction filtration, and drying to obtain the compound of formula (III).

[0036] More preferably, in the preparation method of the compound of formula (III), the separation and purification is carried out by silica gel column chromatography; still more preferably, the eluent for the silica gel column chromatography separation and purification is a mixed solution of a medium-polarity solvent and a low-polarity solvent in a volume ratio of (1-3) : 3; in some preferred embodiments of the present application, the volume ratio of the medium-polarity solvent to the low-polarity solvent is 2:3.

[0037] More preferably, the medium-polarity solvent is selected from at least one of dichloromethane, chloroform, ethyl acetate, and tetrahydrofuran, and the low-polarity solvent is selected from at least one of petroleum ether, cyclohexane, and hexane; still more preferably, the medium-polarity solvent is dichloromethane, and the low-polarity solvent is petroleum ether.

[0038] The fifth aspect of the present application provides a preparation method of the compound of formula (IV) as described above, comprising the following steps:

[0039] The carbon-nitrogen coupling reaction of 7H-benzo[c]carbazole and 4,4'-dihalogen diphenyl sulfone produces a compound of formula (IV).

[0040] Preferably, in the preparation method of the compound of formula (IV), the halogen group in the 4,4'-dihalogen diphenyl sulfone is selected from any one of F, Cl, Br and I; further preferably, the halogen group in the 4,4'-dihalogen diphenyl sulfone is F.

[0041] Preferably, in the preparation method of the compound of formula (IV), the solvent used in the reaction is N,N'-dimethylformamide (DMF).

[0042] Preferably, in the preparation method of the compound of formula (IV), the base used in the reaction is any one of sodium ethoxide, potassium tert-butoxide (t-BuOK) and sodium hydride; further preferably, the base is potassium tert-butoxide.

[0043] Preferably, in the preparation method of the compound of formula (IV), the molar ratio of 7H-benzo[c]carbazole to 4,4'-dihalogen diphenyl sulfone is (1-6):1; further preferably, the molar ratio of 7H-benzo[c]carbazole to 4,4'-dihalogen diphenyl sulfone is (1-5):1; still further preferably, the molar ratio of 7H-benzo[c]carbazole to 4,4'-dihalogen diphenyl sulfone is (1-4):1; more preferably, the molar ratio of 7H-benzo[c]carbazole to 4,4'-dihalogen diphenyl sulfone is 3:1.

[0044] Preferably, in the preparation method of the compound of formula (IV), the reaction is carried out under a protective atmosphere; further preferably, the reaction is carried out under an argon protective atmosphere.

[0045] Preferably, in the preparation method of the compound of formula (IV), the reaction temperature is 100-180℃; further preferably, the reaction temperature is 120-170℃; still further preferably, the reaction temperature is 140-160℃; in some preferred embodiments of the present application, the reaction temperature is 150℃.

[0046] Preferably, in the preparation method of the compound of formula (IV), the reaction time is 12-48h; further preferably, the reaction time is 18-30h; still further preferably, the reaction time is 22-26h; in some preferred embodiments of the present application, the reaction time is 24h.

[0047] Preferably, in the preparation method of the compound of formula (IV), after the reaction, the product is further subjected to separation and purification, reprecipitation, suction filtration and drying to obtain the compound of formula (IV).

[0048] Further preferably, in the preparation method of the compound of formula (IV), the separation and purification are performed by silica gel column chromatography; further preferably, the eluent of the silica gel column chromatography is a mixed solution of a medium-polarity solvent and a low-polarity solvent in a volume ratio of (1-3) : 3; in some preferred embodiments of the present application, the volume ratio of the medium-polarity solvent to the low-polarity solvent is 2:3.

[0049] Further preferably, the medium-polarity solvent is at least one selected from dichloromethane, trichloromethane, ethyl acetate, and tetrahydrofuran, and the low-polarity solvent is at least one selected from petroleum ether, cyclohexane, and hexane; further preferably, the medium-polarity solvent is dichloromethane, and the low-polarity solvent is petroleum ether.

[0050] The sixth aspect of the present application provides a preparation method of a compound of formula (V), comprising the following steps:

[0051] The 7H-benzo[c]carbazole and the 4,4'-dihalogenophenyl ketone are mixed to perform a carbon-nitrogen coupling reaction to obtain the compound of formula (V).

[0052] Preferably, in the preparation method of the compound of formula (V), the halogen group in the 4,4'-dihalogenophenyl ketone is any one selected from F, Cl, Br, and I; further preferably, the halogen group in the 4,4'-dihalogenophenyl ketone is F.

[0053] Preferably, in the preparation method of the compound of formula (V), the solvent used in the reaction is N,N'-dimethylformamide (DMF).

[0054] Preferably, in the preparation method of the compound of formula (V), the base used in the reaction is any one of sodium ethoxide, potassium tert-butoxide (t-BuOK), and sodium hydride; further preferably, the base is potassium tert-butoxide.

[0055] Preferably, in the preparation method of the compound of formula (V), the molar ratio of the 7H-benzo[c]carbazole to the 4,4'-dihalogenophenyl ketone is (1-6) : 1; further preferably, the molar ratio of the 7H-benzo[c]carbazole to the 4,4'-dihalogenophenyl ketone is (1-5) : 1; further preferably, the molar ratio of the 7H-benzo[c]carbazole to the 4,4'-dihalogenophenyl ketone is (1-4) : 1; further preferably, the molar ratio of the 7H-benzo[c]carbazole to the 4,4'-dihalogenophenyl ketone is 2.2:1.

[0056] Preferably, in the preparation method of the compound of formula (V), the reaction is performed under a protective atmosphere; further preferably, the reaction is performed under an argon protective atmosphere.

[0057] Preferably, the reaction temperature in the preparation method of the compound of formula (V) is 100-180℃; more preferably, the reaction temperature is 120-170℃; still more preferably, the reaction temperature is 140-160℃; in some preferred embodiments of the present application, the reaction temperature is 150℃.

[0058] Preferably, the reaction time in the preparation method of the compound of formula (V) is 2-24h; more preferably, the reaction time is 4-16h; still more preferably, the reaction time is 6-10h; in some preferred embodiments of the present application, the reaction time is 7h.

[0059] Preferably, the preparation method of the compound of formula (V) further comprises separation and purification, re-precipitation, suction filtration and drying of the product after the reaction.

[0060] More preferably, the separation and purification in the preparation method of the compound of formula (V) is carried out by silica gel column chromatography; still more preferably, the eluent for the silica gel column chromatography is a mixture of a medium-polarity solvent and a low-polarity solvent in a volume ratio of (1-3) : 3; in some preferred embodiments of the present application, the volume ratio of the medium-polarity solvent to the low-polarity solvent is 2:3.

[0061] More preferably, the medium-polarity solvent is at least one selected from dichloromethane, trichloromethane, ethyl acetate and tetrahydrofuran, and the low-polarity solvent is at least one selected from petroleum ether, cyclohexane and hexane; still more preferably, the medium-polarity solvent is dichloromethane and the low-polarity solvent is petroleum ether.

[0062] The seventh aspect of the present application provides applications of the above-mentioned photo-activated organic long-persistence material in anti-counterfeiting, data encryption and photoprinting.

[0063] The present application has the following advantages:

[0064] The inventors have found that the compounds of formula (I)-(V) can be applied in photo-activated long-persistence materials, and as guest components of photo-activated long-persistence materials, they have high efficiency in generating triplet excitons and strong ability in transferring triplet exciton energy to oxygen molecules. The long-persistence material prepared by doping them in epoxy polymers has a short photo-activation process, and the activated material can be restored to a state without long-persistence emission by heating at 90-120℃ for 6-45min and cooling to room temperature, thus effectively overcoming the shortcomings of long activation time and difficulty in restoring to the unactivated state of the current photo-activated long-persistence materials.

[0065] The light-activated long afterglow material of the present application can effectively inhibit the penetration of solvent molecules at room temperature, and can produce significant long afterglow luminescence even after being soaked in water, concentrated hydrochloric acid, lye and organic solvents for more than 12 hours after light activation, which can solve the problem of instability of long afterglow luminescence performance of the current polymer-based long afterglow material in air and in a solvent atmosphere. The prepared material not only has the characteristics of reversible light-activated long afterglow luminescence, but also has long afterglow luminescence life, high efficiency, adjustable color and good stability after activation, so the material has strong practicability in the fields of anti-counterfeiting, data encryption, optical printing and the like. BRIEF DESCRIPTION OF DRAWINGS

[0066] Figure 1 The nuclear magnetic hydrogen spectrum of formula (III) in Example 3 of the present application.

[0067] Figure 2 The high-resolution mass spectrum of formula (III) in Example 3 of the present application.

[0068] Figure 3 The nuclear magnetic hydrogen spectrum of formula (IV) in Example 4 of the present application.

[0069] Figure 4 The high-resolution mass spectrum of formula (IV) in Example 4 of the present application.

[0070] Figure 5 The nuclear magnetic hydrogen spectrum of formula (V) in Example 5 of the present application.

[0071] Figure 6 The high-resolution mass spectrum of formula (V) in Example 5 of the present application.

[0072] Figure 7 The nuclear magnetic hydrogen spectrum of formula (VII) in Example 7 of the present application.

[0073] Figure 8 The relationship diagram of light irradiation time and afterglow intensity of the long afterglow material prepared in Examples 1-5 of the present application.

[0074] Figure 9 The steady-state spectrum diagram of the long afterglow material prepared in Example 1 of the present application before and after light activation.

[0075] Figure 10 The delay spectrum diagram of the long afterglow material prepared in Examples 1-2 of the present application after light activation.

[0076] Figure 11 The delay spectrum diagram of the long afterglow material prepared in Examples 3-5 of the present application after light activation.

[0077] Figure 12 The room temperature phosphorescence decay curve of the long afterglow material prepared in Example 1 of the present application before and after light activation.

[0078] Figure 13 The steady-state luminescence photos of the long afterglow material prepared in Example 1 of the present application before and after being activated under the irradiation of 365 nm ultraviolet lamp, and the afterglow photos after being photo-activated.

[0079] Figure 14 The photos of the photo-activated long afterglow luminescence and the deactivation process cycle of the long afterglow material prepared in Example 1 of the present application.

[0080] Figure 15 The phosphorescence intensity, phosphorescence decay curve and time delay spectrum of the photo-activated long afterglow luminescence and the deactivation process cycle of the long afterglow material prepared in Example 1 of the present application.

[0081] Figure 16 The long afterglow luminescence of the long afterglow material prepared in Example 1 of the present application after being activated and then soaked in different solvents for different time.

[0082] Figure 17 The photo printing, anti-counterfeiting and information encryption application display of the long afterglow material prepared in Example 1 of the present application. DETAILED DESCRIPTION

[0083] The concept and technical effects of the present application will be described below in combination with examples, so as to fully understand the purpose, features and effects of the present application. Obviously, the described examples are only a part of the examples of the present application, but not all the examples. Based on the examples of the present application, other examples obtained by those skilled in the art without creative labor are within the protection scope of the present application.

[0084] Example 1

[0085] A preparation method of a photo-activated organic long afterglow material containing a compound of formula (I), comprising the following steps:

[0086] The compound of formula (I) (phenoxazine) (0.40 mg, 0.0022 mmol), bisphenol A diglycidyl ether (300.00 mg, 0.88 mmol) and 1,3-propanediamine were taken in a 1.5 mL transparent sample tube; the above mixture was ultrasonicated to be clear and transparent at room temperature, injected into a mold, and cured at 90°C for 2 hours to obtain a polymer material with a molar fraction of 0.25% of the compound of formula (I).

[0087] The compound of formula (I) is obtained by commercial purchase, and its structure is as follows:

[0088]

[0089] Example 2

[0090] A method for preparing a photo-activated organic long afterglow material comprising a compound of formula (II), comprising the steps of:

[0091] (1) Under argon protection, phenoxazine (1.00 g, 5.46 mmol) and tetrahydrofuran (20 mL) were added to a three-necked flask, then sodium hydride (0.66 g, 13.47 mmol) was added, stirred at room temperature for 30 min, then ethyl bromide (0.60 g, 5.55 mmol) was added dropwise, the temperature was raised to 80 °C, and the reaction was stirred at 80 °C for 24 h. After the reaction was completed, the reaction solution was cooled to room temperature, the solvent was removed, and the crude product was purified by silica gel column chromatography with a mixture of dichloromethane and petroleum ether (1:2, by volume) as the mobile phase. The obtained product was re-precipitated with methanol and dichloromethane, filtered, and dried under vacuum to obtain 0.60 g of white solid powder (compound of formula (II)), with a yield of 52%.

[0092] The reaction formula is as follows:

[0093]

[0094] (2) In a 1.5 mL transparent sample tube, the compound of formula (II) (10-ethylphenoxazine) prepared in step (1) (0.46 mg, 0.0022 mmol), bisphenol A diglycidyl ether (300.00 mg, 0.88 mmol), and 1,3-propanediamine were taken; the mixture was ultrasonicated at room temperature until it became clear and transparent, and then poured into a mold, and cured at 90 °C for 2 h to obtain a polymer material with a molar fraction of the compound of formula (II) of 0.25%.

[0095] Example 3

[0096] A method for preparing a photo-activated organic long afterglow material comprising a compound of formula (III), comprising the steps of:

[0097] (1) Under argon protection, 4-bromoethyl benzoate (0.46 g, 2.00 mmol) and 7H-benzo[c]carbazole (0.43 g, 2.00 mmol) were added to a three-necked flask, then Ruphos (100 mg) and potassium phosphate (3.00 g, 14.1 mmol) were added, dissolved in 20 mL of toluene, stirred at room temperature for 30 min, then Pd2(dba)3(50 mg) was added, the temperature was raised to 120 °C, and the reaction was stirred at 120 °C for 30 h. After the reaction was completed, the reaction solution was cooled to room temperature, the solvent was removed, and the crude product was purified by silica gel column chromatography with a mixture of dichloromethane and petroleum ether (5:6, by volume) as the mobile phase. The obtained product was re-precipitated with methanol and dichloromethane, filtered, and dried under vacuum to obtain 0.60 g of white solid powder (product of formula III), with a yield of 86%.

[0098] The reaction formula is as follows:

[0099]

[0100] (2) Take the compound of formula (III) (0.32 mg, 0.0009 mmol), bisphenol A diglycidyl ether (300.00 mg, 0.88 mmol) and 1,3-propanediamine in a 1.5 mL transparent sample tube. The above mixture is ultrasonicated to be clear and transparent at room temperature, injected into a mold, and cured at 90°C for 2 hours to obtain a polymer material with a molar fraction of 0.10% of the compound of formula (III).

[0101] The nuclear magnetic hydrogen spectrum and mass spectrum of the compound of formula (III) prepared in this example are shown in Figure 1 , Figure 2 respectively.

[0102] Example 4

[0103] A method for preparing a photo-activated organic long afterglow material comprising a compound of formula (IV) comprises the following steps:

[0104] (1) Under argon protection, 7H-benzo[c]carbazole (0.77 g, 3.54 mmol) and N,N"-dimethylformamide (DMF, 10 mL) are added to a three-necked bottle, potassium tert-butoxide (t-BuOK, 0.79 g, 7.08 mmol) is added, stirred at room temperature for 20 min, 4,4'-difluorodiphenyl sulfone (0.30 g, 1.18 mmol) is added, the temperature is raised to 150°C, and stirred at 150°C, and refluxed for 24 hours. After the reaction is completed, the reaction solution is cooled to room temperature, slowly poured into 200 mL ice-salt water, suction filtered, and the solid crude product is washed with deionized water for 3 times. Subsequently, the crude product is purified by silica gel column chromatography with a mixed solution of dichloromethane and petroleum ether in a volume ratio of 2:3 as the mobile phase, the obtained product is reprecipitated with petroleum ether and dichloromethane, suction filtered, and vacuum dried to obtain 0.29 g of white solid powder (product of formula IV compound) with a yield of 38%.

[0105] The reaction formula is as follows:

[0106]

[0107] (2) Take the compound of formula (IV) (0.58 mg, 0.0009 mmol), bisphenol A diglycidyl ether (300.00 mg, 0.88 mmol) and 1,3-propanediamine in a 1.5 mL transparent sample tube. The above mixture is ultrasonicated to be clear and transparent at room temperature, injected into a mold, and cured at 90°C for 2 hours to obtain a polymer material with a molar fraction of 0.10% of the compound of formula (IV).

[0108] The nuclear magnetic hydrogen spectrum and mass spectrum of the compound of formula (IV) prepared in this example are shown in Figure 3 , Figure 4 .

[0109] Example 5

[0110] A method for preparing a photo-activated organic long afterglow material comprising a compound of formula (V) comprises the following steps:

[0111] (1) Under argon protection, 7H-benzo[c]carbazole (0.40 g, 1.84 mmol) and N,N'-dimethylformamide (DMF, 10 mL) were added to a three-necked flask, potassium tert-butoxide (t-BuOK, 0.35 g, 3.12 mmol) was added, and stirring was performed at 60°C for 10 min, 4,4'-difluorobenzophenone (0.18 g, 0.82 mmol) was added, the temperature was raised to 150°C, and stirring was performed at 150°C, and reflux reaction was performed for 7 h. After the reaction was completed, the reaction liquid was cooled to room temperature, slowly poured into 200 mL of ice-salt water, suction filtration was performed, and the solid crude product was washed with deionized water for 3 times. Subsequently, the crude product was purified by silica gel column chromatography with a mixed solution of dichloromethane and petroleum ether in a volume ratio of 2:3 as the mobile phase, the obtained product was reprecipitated with petroleum ether and dichloromethane, suction filtration was performed, and vacuum drying was performed to obtain 0.22 g of white solid powder (product compound of formula V), and the yield was 44%.

[0112] The reaction formula is as follows:

[0113]

[0114] (2) The compound of formula (V) (0.55 mg, 0.0009 mmol), bisphenol A diglycidyl ether (300.00 mg, 0.88 mmol), and 1,3-propanediamine were taken in a 1.5 mL transparent sample tube. The mixture was ultrasonically treated to be clear and transparent at room temperature, injected into a mold, and cured at 90°C for 2 h to obtain a polymer material with a molar fraction of the compound of formula (V) of 0.10%.

[0115] The nuclear magnetic hydrogen spectrum and mass spectrum of the compound of formula (V) prepared in this example are shown in Figure 5 , Figure 6 .

[0116] Example 6

[0117] A method for preparing an epoxy polymer material comprising a compound of formula (VI) comprises the following steps:

[0118] A compound of formula (VI) (0.73 mg, 0.0022 mmol), bisphenol A diglycidyl ether (300.00 mg, 0.88 mmol) and 1,3-propanediamine were taken in a 1.5 mL clear sample tube. The above mixture was sonicated to clear transparency at room temperature, injected into a mold, and cured at 90 °C for 2 hours to obtain a polymer material with a mole fraction of 0.25% of the compound of formula (VI).

[0119] The compound of formula (VI) was obtained by commercial purchase, and its structure is as follows:

[0120]

[0121] Example 7

[0122] A method for preparing an epoxy polymer material containing a compound of formula (VII) includes the following steps:

[0123] (1) Phenoxazine (0.50 g, 2.72 mmol), 4-bromobenzonitrile (0.60 g, 3.30 mmol), tri-tert-butylphosphine tetrafluoroborate (0.118 g, 0.41 mmol), potassium carbonate (0.10 g, 0.72 mmol), potassium phosphate (1.04 g, 4.9 mmol) were added to a three-necked flask under argon protection, dissolved in 16 mL of toluene, stirred at room temperature for 30 min, then palladium acetate (50 mg) was added, the temperature was raised to 120 °C, and stirred at 120 °C for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography with a mixture of dichloromethane and petroleum ether (1:2, by volume) as the mobile phase. After the solvent was removed by rotary evaporation and vacuum drying, 0.10 g of white solid powder (product, compound of formula VII) was obtained, with a yield of 13%.

[0124] The reaction formula is as follows:

[0125]

[0126] (2) A compound of formula (VII) (0.63 mg, 0.0022 mmol), bisphenol A diglycidyl ether (300.00 mg, 0.88 mmol) and 1,3-propanediamine were taken in a 1.5 mL clear sample tube. The above mixture was sonicated to clear transparency at room temperature, injected into a mold, and cured at 90 °C for 2 hours to obtain a polymer material with a mole fraction of 0.25% of the compound of formula (VII).

[0127] The nuclear magnetic resonance spectrum of the compound of formula (VII) prepared in this example is shown in Figure 7

[0128] Performance test: ​

[0129] The materials prepared in Examples 1-7 were subjected to performance tests, mainly investigating the photoactivation performance, long afterglow luminescence performance, solvent resistance, etc. of the target materials. The luminescence performance tests of the above-mentioned materials were performed on an Edinburgh FLS980 steady-state transient fluorescence spectrometer with an integrating sphere and an Ocean Optics QE65 Pro CCD fiber spectrometer, and the test results are shown in Table 1 below. The light irradiation time vs. afterglow intensity graph of the polymer materials in Examples 1-5, the steady-state spectrum graph before and after photoactivation, the delayed spectrum graph after photoactivation, the room temperature phosphorescence decay curve before and after photoactivation, the luminescence and afterglow photos before and after activation under 365 nm ultraviolet light irradiation, the photoactivation long afterglow luminescence and its deactivation process cycle, the long afterglow luminescence after activation and soaking in different solvents for different times, and the light printing application display, etc. are shown in Figs. 1-5, respectively. Figures 8-17 .

[0130] Figures 1-7 The nuclear magnetic resonance hydrogen spectrum and high-resolution mass spectrum shown in Figs. 1-5 confirm the structures and sample purity of the compounds of formulae (III), (IV), (V), (VII).

[0131] As can be seen from Table 1 and Figures 8-13 the long afterglow materials prepared in Examples 1-5 do not have super-long lifetime phosphorescence emission properties in the initial state, and their lifetimes are all below 10 ms. After being irradiated and activated by 365 nm ultraviolet light for 90-720 s, respectively, the prepared materials can all produce significant long afterglow luminescence, and the afterglow lifetime can be up to 1.906 s, and the efficiency can be up to 10.81%.

[0132] Table 1: Optical physical property data of organic long afterglow materials in examples

[0133]

[0134] Notes: a the lifetime at 536 nm, b heating at 90°C, c heating at 120°C, d the phosphorescence lifetime at 476 nm at room temperature

[0135] As can be seen from Table 1 and Figures 14-15 the organic long afterglow material prepared in Example 1 can be restored to a state without long afterglow luminescence after being photoactivated, heated at 90-120°C for 6-45 min and cooled to room temperature, and the activation and deactivation processes thereof can be cycled multiple times.

[0136] The above results show that the prepared materials all have the photoactivation long afterglow luminescence characteristics, the activation time is relatively fast, only 90-720 s is needed to complete, and the activation time, long afterglow luminescence performance and deactivation time can be regulated by changing the chemical structure of the guest molecules.

[0137] Meanwhile, as shown in Table 1, at room temperature, Example 6 only emits standard fluorescence, and Example 7 only emits short-lived room-temperature phosphorescence; neither exhibits the photoactivated long-lasting luminescence characteristic. This result demonstrates that only by doping epoxy polymers with carefully selected and designed compounds can reversibly photoactivated long-lasting luminescence materials be prepared.

[0138] Depend on Figure 16 It can be seen that the organic long afterglow material prepared in Example 1 can still emit significant long afterglow after being immersed in solvents such as water, concentrated hydrochloric acid (mass fraction 36%-38%), sodium hydroxide aqueous solution (1 mol / L), n-hexane, toluene, and tetrahydrofuran for 12 hours after activation. It can even maintain good long afterglow luminescence performance after being immersed in the solvent for 4 weeks, indicating that it has excellent stability.

[0139] Depend on Figure 17 It can be seen that by utilizing the reversible light-activated long-lasting luminescence properties of the material prepared in Example 1, the desired afterglow luminescence pattern can be clearly printed on the material using light. Furthermore, different patterns can be easily reprinted or different information can be written after thermal erasure (deactivation), thus achieving optical printing and erasing functions. It should be noted that the pattern is invisible under ambient light and only appears in the form of afterglow luminescence after ultraviolet light excitation and removal of the excitation source. These results demonstrate that the prepared long-lasting luminescence material has strong practicality in the fields of optical printing, anti-counterfeiting, and information encryption.

[0140] While the embodiments of the present invention have been described in detail above, the present invention is not limited to the embodiments described above. Various modifications may be made within the scope of knowledge possessed by a person skilled in the art without departing from the spirit of the present invention. Furthermore, the embodiments of the present invention and the features thereof may be combined with one another unless there is a conflict.

Claims

1. Use of compounds of formula (III), formula (IV), and formula (V) in photoactivated organic long afterglow materials; The structural formulas of the compounds of formula (III), formula (IV) and formula (V) are shown below: Formula (III) Formula (IV) Formula (V).

2. A light-activated organic long afterglow material, characterized in that: The light-activated organic long afterglow material includes a host component and a guest component doped in the host component, the host component is selected from epoxy polymers, and the guest component is selected from at least one of the compounds of formula (III), formula (IV), and formula (V) according to claim 1.

3. The light-activated organic long afterglow material according to claim 2, characterized in that: The molar percentage of the guest component in the light-activated organic long afterglow material is 0.001-5%.

4. The light-activated organic long afterglow material according to claim 2, characterized in that: The epoxy polymer is prepared by polymerization of bisphenol A diglycidyl ether and a curing agent.

5. The light-activated organic long afterglow material according to claim 4, characterized in that: The molar ratio of the bisphenol A diglycidyl ether, the guest component and the curing agent is 1: (0.0001-0.05): (0.5-2).

6. The method for preparing the light-activated organic long afterglow material according to claim 4 or 5, characterized in that: The following steps are involved: Bisphenol A diglycidyl ether, a guest component, and a curing agent are mixed and stirred, and then cured to obtain the light-activated organic long afterglow material.

7. Use of the light-activated organic long afterglow material according to any one of claims 2 to 5 in anti-counterfeiting, data encryption, and optical printing.

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