An ultralong organic high-temperature phosphorescent doped luminescent material and a preparation method thereof

Abstract

The application discloses a kind of super-long organic high-temperature phosphorescent doped luminescent materials and preparation method thereof, the luminescent material is with planar rigid molecule as guest, rigid polymer is host to realize super-long high-temperature phosphorescent emission;Planar rigid structure can resist the thermal vibration of guest at high temperature, and the rigidity of host further solidifies the high-temperature resistance of guest, finally, this double rigidity activates the super-long high-temperature phosphorescent performance of doped system.The doped material has the longest super-long afterglow of 40s at 20 DEG C, the lifetime is 4.18s, has the longest super-long afterglow of 20s at 100 DEG C, the lifetime is 4.18s, has about 6s of the longest super-long afterglow at 140 DEG C, the lifetime is 0.77s, even has 1s visible afterglow at 160 DEG C high temperature.

Description

Technical Field

[0001] This invention relates to the field of optoelectronic materials technology, and more specifically to an ultralong organic high-temperature phosphorescent doped luminescent material and its preparation method. Background Technology

[0002] Phosphorescent materials are materials that emit phosphorescence when excited by electromagnetic radiation and ion beams. Generally, light emitted after excitation ceases is considered phosphorescence. The process of light radiation with minimal heat that occurs when the excited object returns to equilibrium is called fluorescence. The emission of light from long-afterglow luminescent materials is a typical example of phosphorescence. Phosphorescent materials are available in various forms, including single crystals, thin films, microcrystalline powders, and microcrystalline glass. Common types include sulfides, oxides, group II-IV and IV-V compounds, and rare-earth luminescent materials. They can be used in displays, fluorescent lamps, ionizing radiation detection, aircraft instrument panels, lasers, and infrared night vision devices, showing broad application prospects as display materials.

[0003] Compared to inorganic noble metal phosphorescent materials, organic phosphorescent materials have advantages such as low cost, high plasticity, and low toxicity, which has attracted widespread attention from scientists in recent years. Among them, the host-guest polymer doping strategy is widely regarded as one of the effective methods for constructing room temperature phosphorescent materials. Currently, organic room temperature phosphorescent (RTP) materials with long afterglow phenomena are attracting much attention from researchers, and have unique advantages in fields such as anti-counterfeiting, biological diagnosis and treatment, and optoelectronic devices.

[0004] After organic materials absorb excitation energy, electrons transition from the ground state to the excited state. However, the excited state energy is unstable, and due to molecular motion, it easily returns to the ground state in the form of thermal energy / non-radiative energy. More seriously, high temperatures undoubtedly accelerate molecular motion. Therefore, triplet excitons formed by singlet excitons crossing between systems are extremely sensitive to temperature and are more prone to thermal deactivation, causing the afterglow to disappear rapidly at high temperatures. The defect of phosphorescence emission being intolerant to high temperatures greatly limits the application range of organic materials. Therefore, it is crucial to study strategies for constructing ultralong organic high-temperature phosphorescent materials. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the purpose of this invention is to provide a doped luminescent material with ultralong organic high-temperature phosphorescence and its preparation method. The luminescent material is resistant to high temperature and has a long afterglow.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] An ultra-long organic high-temperature phosphorescent doped luminescent material comprises the following components in parts by weight:

[0008] 1-3 parts of the guest compound;

[0009] 500-1500 parts of the main polymer;

[0010] The guest compound is a planar rigid organic molecule containing at least three benzene ring structures;

[0011] The main polymer is polyvinylpyrrolidone.

[0012] Polyvinylpyrrolidone is readily available, inexpensive, and easy to prepare. It also has a very rigid structure and a glass transition temperature of 180°C, making it more suitable for high-temperature resistance.

[0013] As a further improvement of the present invention

[0014] The guest compound is benzo[a]carbazole and its derivatives;

[0015] The number average molecular weight of polyvinylpyrrolidone ranges from 50,000 to 400,000.

[0016] As a further improvement of the present invention, the guest compound is at least one selected from 1, 9H-dibenzo[a,c]carbazole, 9-methyl-dibenzo[a,c]carbazole, 9-n-butyl-dibenzo[a,c]carbazole, 9-benzyl-dibenzo[a,c]carbazole, 7H-benzo[c]carbazole, 7-methyl-benzo[c]carbazole, 7H-dibenzo[c,g]carbazole and 7-methyl-dibenzo[c,g]carbazole;

[0017] Its corresponding structural formula is:

[0018]

[0019] Among them, 7H-benzo[c]carbazole (purchased from Bid Pharmaceuticals); 7H-dibenzo[c,g]carbazole (purchased from Bid Pharmaceuticals);

[0020] As a further improvement of the present invention

[0021] The preparation method of the 1,9H-dibenzo[a,c]carbazole is as follows:

[0022] Indole-2-carboxylic acid, dibenzo[b,d]iodocyclopentane-5-onium trifluoromethanesulfonate (purchased from Bid Pharmaceutical), palladium acetate, potassium carbonate and acetic acid were mixed evenly and then reacted at 130-160℃ for 10-15 hours. After the reaction was completed, the mixture was separated and purified to obtain the product.

[0023] As a further improvement of the present invention, the molar ratio between indole-2-carboxylic acid and dibenzo[b,d]iodocyclopentane-5-onium trifluoromethanesulfonate is 1:1.1-1.6.

[0024] Divalent palladium is activated by CH4 of indole-2-carboxylic acid to obtain a palladium-intercalated intermediate, which is then reacted with dibenzo[b,d]iodocyclopentane-5-onium trifluoromethanesulfonate to open the ring and form a tetravalent palladium intermediate. Through successive decarboxylation, oxidative addition and reductive elimination, the corresponding product is obtained. This preparation method is simple to operate and has a high yield.

[0025] As a further improvement of the present invention, the preparation method of the 9-benzyl-dibenzo[a,c]carbazole is as follows:

[0026] A mixture of compound NaH,1,9H-dibenzo[a,c]carbazole and N,N-dimethylformamide was stirred in an ice bath for 5-20 minutes, and then stirred at room temperature for 20-40 minutes. After stirring, a mixed solution of 4-bromobenzyl bromide and N,N-dimethylformamide was added dropwise to react. The reaction was carried out at room temperature for 10-20 hours. After the reaction was completed, the product was separated and purified to obtain the product.

[0027] As a further improvement of the present invention, the molar ratio between compound NaH and 1,9H-dibenzo[a,c]carbazole is 2-5:1.

[0028] As a further improvement of the present invention, the method for preparing the luminescent material is as follows: according to the set weight parts, the raw materials are prepared, the guest compound and the host polymer are dissolved in dichloromethane (solvent) and stirred and mixed. After being mixed evenly, the mixture is first treated at a temperature of 30-50°C for 1-3 hours, and then treated at a temperature of 80-120°C for 12 hours to obtain the luminescent material.

[0029] The beneficial effects of this invention are as follows: We selected a series of rigid molecules with almost entirely planar molecular configurations as guests. The planar structure of these rigid molecules remains unchanged regardless of external or internal forces, always maintaining its planar structure. This planar configuration minimizes molecular vibration and rotation, reducing the triplet excitons consumed by non-radiative transitions. This allows more triplet excitons to return to the ground state via radiative transitions, enhancing phosphorescence performance. Therefore, the rigid configuration is beneficial for increasing phosphorescence lifetime and intensity, and extending afterglow time and brightness. Secondly, we selected polyvinylpyrrolidone (PVP) with a rigid structure and a glass transition temperature of 180°C as the host. PPVP is readily available, inexpensive, and easy to prepare. Its inherent rigidity further suppresses the molecular motion of the guest molecules. Combined with its ultra-high glass transition temperature, it maintains good molecular solidification even at high temperatures, suppressing the vibration and rotation of the guest molecules doped within it, reducing non-radiative transitions in the doped material, and thus improving phosphorescence performance. This dual rigidity enables the doped material to exhibit excellent ultra-long organic high-temperature phosphorescence properties, allowing afterglow to still be observed at 160°C. Attached Figure Description

[0030] Figure 1 The NMR spectrum of the guest compound 9H-dibenzo[a,c]carbazole in Example 1 of this invention;

[0031] Figure 2 The NMR spectrum of 9-methyl-dibenzo[a,c]carbazole, the guest compound of Example 2 of this invention;

[0032] Figure 3 The NMR spectrum of 9-n-butyl-dibenzo[a,c]carbazole, the guest compound of Example 2 of this invention;

[0033] Figure 4 The NMR spectrum of 9-benzyl-dibenzo[a,c]carbazole, the guest compound of Example 3 of this invention;

[0034] Figure 5 The NMR spectrum of the guest compound 7H-benzo[c]carbazole in Example 2 of this invention;

[0035] Figure 6 The NMR spectrum of 7-methyl-benzo[c]carbazole, the guest compound of Example 2 of this invention;

[0036] Figure 7 The NMR spectrum of the guest compound 7H-dibenzo[c,g]carbazole in Example 2 of this invention;

[0037] Figure 8 The NMR spectrum of 7-methyl-dibenzo[c,g]carbazole, the guest compound of Example 2 of this invention;

[0038] Figure 9 This is a comparison of afterglow at different temperatures after irradiation with a 380nm ultraviolet lamp in Embodiment 4 of the present invention;

[0039] Figure 10 This is a comparison of afterglow at different temperatures after irradiation with a 380nm ultraviolet lamp in Embodiment 5 of the present invention;

[0040] Figure 11 This is a comparison of afterglow at different temperatures after irradiation with a 380nm ultraviolet lamp in Embodiment Six of the present invention;

[0041] Figure 12 This is a comparison of afterglow at different temperatures after irradiation with a 380nm ultraviolet lamp in Embodiment 7 of the present invention;

[0042] Figure 13 This is a comparison of afterglow at different temperatures after irradiation with a 380nm ultraviolet lamp in Embodiment 8 of the present invention;

[0043] Figure 14 This is a comparison of afterglow at different temperatures after irradiation with a 380nm ultraviolet lamp in Embodiment 9 of the present invention;

[0044] Figure 15 This is a comparison of afterglow at different temperatures after irradiation with a 380nm ultraviolet lamp in Embodiment 10 of the present invention;

[0045] Figure 16 This is a comparison of afterglow at different temperatures after irradiation with a 380nm ultraviolet lamp in Embodiment 11 of the present invention. Detailed Implementation

[0046] The present invention will now be described in further detail with reference to the embodiments shown in the accompanying drawings.

[0047] Example 1: Preparation of Compound 1

[0048] A mixture of indole-2-carboxylic acid (322.2 mg, 2 mmol), cyclodiethyliodonium salt (1027.2 mg, 2.4 mmol), palladium acetate (44.8 mg, 0.2 mmol), potassium carbonate (607.3 mg, 4.4 mmol), and acetic acid (12 mL) was stirred at 145 °C for 12 h. After cooling to room temperature, the reaction mixture was poured into dichloromethane (100 mL), washed three times with water (50 mL), and then dried over anhydrous sodium sulfate. After solvent removal under reduced pressure, the residue was purified by silica gel flash chromatography to give compound 1.

[0049] The reaction equation is as follows:

[0050]

[0051] Example 2:

[0052] Preparation of guest compounds 2, 3, 6, and 8:

[0053] A mixture of the corresponding carbazole (1 mmol) and potassium tert-butoxide (168 mg, 1.5 mmol) was dissolved in THF and heated to 50 °C, followed by the addition of the corresponding iodide (1.4 mmol). After cooling to room temperature, the reaction mixture was poured into dichloromethane (100 mL), washed three times with water (50 mL), and then dried over anhydrous sodium sulfate. After solvent removal under reduced pressure, the residue was purified by silica gel flash chromatography to give the target products, guest compounds 2, 3, 6, and 8.

[0054] The reaction equation is as follows:

[0055]

[0056] Example 3: Preparation of Guest Compound 3

[0057] Sodium hydride (120 mg, 60% dispersed in mineral oil, 3 mmol) and compound 1 (268 mg, 1 mmol) were placed in a round-bottom flask, followed by 4 mL of N,N-dimethylformamide solution, and stirred until homogeneous. The mixture was then stirred in an ice bath for 10 minutes, followed by stirring at room temperature for 30 minutes. After half an hour, a mixture of 4-bromobenzyl bromide (205 mg, 1.2 mmol) and 4 mL of N,N-dimethylformamide solution was added dropwise to the round-bottom flask. The reaction mixture was stirred overnight at room temperature. After water quenching, the reaction mixture was poured into dichloromethane (100 mL), washed three times with water (50 mL), and then dried over anhydrous sodium sulfate. After solvent removal under reduced pressure, the residue was purified by silica gel flash chromatography to obtain the target product compound 3.

[0058] The reaction equation is as follows:

[0059]

[0060] Guest compounds 1-8 were then subjected to NMR analysis, such as... Figures 1 to 8 As shown, Figure 1 In the spectrum, 'a' represents the proton NMR spectrum of guest compound 1. Figure 1 In the image, b is the carbon spectrum of guest compound 1; Figure 2 In the spectrum, 'a' represents the proton NMR spectrum of guest compound 2. Figure 2 In the image, b represents the carbon spectrum of guest compound 2. Figure 3 In the spectrum, 'a' represents the proton NMR spectrum of guest compound 3. Figure 3 In the image, b is the carbon spectrum of guest compound 3; Figure 4 In the spectrum, 'a' represents the proton NMR spectrum of guest compound 4. Figure 4 b is the carbon spectrum of guest compound 4; Figure 5 In the spectrum, 'a' represents the proton NMR spectrum of guest compound 5. Figure 5 b is the carbon spectrum of guest compound 5; Figure 6 In the spectrum, 'a' represents the proton NMR spectrum of guest compound 6. Figure 6 b is the carbon spectrum of guest compound 6; Figure 7 In the spectrum, 'a' represents the proton NMR spectrum of guest compound 7. Figure 7 In the image, b is the carbon spectrum of guest compound 7; Figure 8 In the spectrum, 'a' represents the proton NMR spectrum of guest compound 8. Figure 8 In the image, b is the carbon spectrum of guest compound 8.

[0061] according to Figures 1 to 8 As shown, the synthesized compound matches the expectation, and the target compound has been synthesized.

[0062] Example 4:

[0063] Guest compound 1 obtained in Example 1 was mixed with the host polymer polyvinylpyrrolidone at a ratio of 1:500. The mixture was dissolved in dichloromethane and sonicated for 20 minutes to ensure complete dissolution and homogeneity of both compounds. The mixture was then poured into a mold and baked in an oven at 40°C for 2 hours, followed by baking at 100°C for 12 hours to obtain a polymer-doped luminescent thin film material. The color change of the luminescent material at different temperatures before and after 60 seconds of 380nm ultraviolet light irradiation is shown. (Refer to...) Figure 9 .

[0064] After activation by a 380nm UV lamp for 60 seconds, the polymer film exhibited blue fluorescence under a 380nm UV lamp at 20°C, followed by a long green afterglow of 40 seconds after the UV lamp was removed, with a lifetime of 4.18 seconds; at 40°C, it exhibited blue fluorescence under a 380nm UV lamp, followed by a green afterglow of 35 seconds after the UV lamp was removed, with a lifetime of 4.09 seconds; at 60°C, it exhibited blue fluorescence under a 380nm UV lamp, followed by a green afterglow of 30 seconds after the UV lamp was removed, with a lifetime of 3.72 seconds; and at 80°C, it exhibited blue fluorescence under a 380nm UV lamp, followed by a green afterglow of 25 seconds after the UV lamp was removed. The fluorescence intensity is as follows: 1.05 seconds; 2.17 seconds; 3.17 seconds; 3.05 seconds; 1.30 seconds; 1.30 seconds; 1.40 seconds; 0.77 seconds; 0.77 seconds; 1.60 seconds; 0.33 seconds. The fluorescence intensity is 3.05 seconds; ...

[0065] temperature Phosphorescence wavelength (nm) Phosphorescent afterglow (s) Phosphorescence lifetime (s) 20℃ 487 / 516 40 4.18 40℃ 486 / 516 35 4.09 60℃ 485 / 515 30 3.72 80℃ 485 / 515 25 3.05 100℃ 484 / 516 20 2.17 120℃ 484 / 515 15 1.30 140℃ 483 / 516 6 0.77 160℃ 484 / 516 1 0.33

[0066] Example 5:

[0067] Guest compound 2 obtained in Example 2 was mixed with the host polymer polyvinylpyrrolidone at a ratio of 1:500. The mixture was dissolved in dichloromethane and sonicated for 20 minutes to ensure complete dissolution and homogeneity of both compounds. The mixture was then poured into a mold and baked in an oven at 40°C for 2 hours, followed by baking at 100°C for 12 hours to obtain a polymer-doped luminescent thin film material. The color change of the luminescent material at different temperatures before and after 60 seconds of 380nm ultraviolet light irradiation is shown. (Refer to...) Figure 10 .

[0068] After activation by a 380nm UV lamp for 60 seconds, the polymer film exhibited blue fluorescence under a 380nm UV lamp at 20°C, followed by a long yellow-green afterglow of 40 seconds after the UV lamp was removed, with a lifetime of 4.12 seconds. At 40°C, it showed blue fluorescence under a 380nm UV lamp, followed by a yellow-green afterglow of 35 seconds, with a lifetime of 3.93 seconds. At 60°C, it showed blue fluorescence under a 380nm UV lamp, followed by a yellow-green afterglow of 30 seconds, with a lifetime of 3.63 seconds. At 80°C, it showed blue fluorescence under a 380nm UV lamp, followed by a yellow-green afterglow of 25 seconds. The fluorescence intensity is as follows: 1.08 seconds; 2.13 seconds; 3.08 seconds; 3.08 seconds; 3.13 seconds; 3.13 seconds; 3.13 seconds; 3.13 seconds; 1.32 seconds; 1.32 seconds; 1.32 seconds; 1.45 seconds; 0.75 seconds; 0.75 seconds; 0.34 seconds. 4.13 seconds; 1.13 seconds; 2.13 seconds; 3.13 seconds; 2.13 seconds; 3.13 seconds; 2.13 seconds; 1.32 seconds; 1.32 seconds; 1.32 seconds; 1.32 seconds; 1.32 seconds; 0.75 seconds; 0.75 seconds; 0.75 seconds; 0.75 seconds; 0.75 seconds; 0.75 seconds; 0.75 seconds; 0.75 seconds; 0.75 seconds; 0.75 seconds; 0.76 seconds; 0.76 seconds; 0.34 seconds; 3.14 seconds; 1.32 seconds; 1.32 seconds; 1.32 seconds; 0.75 seconds; 0.75 seconds; 0.76 ...

[0069] temperature Phosphorescence wavelength (nm) Phosphorescent afterglow (s) Phosphorescence lifetime (s) 20℃ 494 / 525 40 4.12 40℃ 495 / 525 35 3.93 60℃ 495 / 526 30 3.63 80℃ 495 / 525 25 3.08 100℃ 494 / 525 20 2.13 120℃ 496 / 524 15 1.32 140℃ 495 / 523 6 0.75 160℃ 496 / 526 1 0.34

[0070] Example 6:

[0071] Guest compound 3 obtained in Example 2 was mixed with the host polymer polyvinylpyrrolidone at a ratio of 1:500. The mixture was dissolved in dichloromethane and sonicated for 20 minutes to ensure complete dissolution and homogeneity of the guest compound and host polymer. The mixture was then poured into a mold and baked in an oven at 40°C for 2 hours, followed by baking at 100°C for 12 hours to obtain a polymer-doped luminescent thin film material. The color change of the luminescent material at different temperatures before and after 60 seconds of 380nm ultraviolet light irradiation is shown. (Refer to...) Figure 11 .

[0072] After activation by a 380nm UV lamp for 60 seconds, the polymer film exhibited blue fluorescence under a 380nm UV lamp at 20°C, followed by a long yellow-green afterglow of 40 seconds after the UV lamp was removed, with a lifetime of 4.14 seconds; at 40°C, it exhibited blue fluorescence under a 380nm UV lamp, followed by a yellow-green afterglow of 35 seconds, with a lifetime of 3.96 seconds; at 60°C, it exhibited blue fluorescence under a 380nm UV lamp, followed by a yellow-green afterglow of 30 seconds, with a lifetime of 3.53 seconds; and at 80°C, it exhibited blue fluorescence under a 380nm UV lamp, followed by a yellow-green afterglow of 25 seconds. The fluorescence intensity is as follows: 1.95 seconds; 2.16 seconds; 2.16 seconds; 1.22 seconds; 1.22 seconds; 0.74 seconds; 0.32 seconds; 1.32 seconds. At 160°C, it exhibits blue fluorescence under a 380nm UV lamp, followed by a yellow-green afterglow for 1 second after the UV lamp is removed. The fluorescence intensity at 100°C and 380nm UV lamp has a lifetime of 2.95 seconds. At 100°C, it displays blue fluorescence under a 380nm UV lamp, followed by a yellow-green afterglow for 20 seconds after the UV lamp is removed.

[0073] temperature Phosphorescence wavelength (nm) Phosphorescent afterglow (s) Phosphorescence lifetime (s) 20℃ 493 / 525 40 4.14 40℃ 494 / 525 35 3.96 60℃ 495 / 525 30 3.53 80℃ 496 / 526 25 2.95 100℃ 496 / 527 20 2.16 120℃ 496 / 525 15 1.22 140℃ 494 / 524 6 0.74 160℃ 495 / 525 1 0.32

[0074] Example 7:

[0075] Guest compound 4 obtained in Example 3 was mixed with the host polymer polyvinylpyrrolidone at a ratio of 1:500. The mixture was dissolved in dichloromethane and sonicated for 20 minutes to ensure complete dissolution and homogeneity. The mixture was then poured into a mold and baked in an oven at 40°C for 2 hours, followed by baking at 100°C for 12 hours to obtain a polymer-doped luminescent thin film material. The color change of the luminescent material at different temperatures before and after 60 seconds of 380nm ultraviolet light irradiation is shown. (Refer to...) Figure 12 .

[0076] After activation by a 380nm UV lamp for 60 seconds, the polymer film exhibited blue fluorescence under the same lamp at 20°C for 36 seconds, followed by a long yellow-green afterglow of 36 seconds after the UV lamp was removed, with a lifetime of 3.88 seconds. At 40°C, it showed blue fluorescence under the same lamp, followed by a yellow-green afterglow of 31 seconds, with a lifetime of 3.45 seconds. At 60°C, it showed blue fluorescence under the same lamp, followed by a yellow-green afterglow of 26 seconds, with a lifetime of 3.09 seconds. At 80°C, it showed blue fluorescence under the same lamp, followed by a yellow-green afterglow of 20 seconds. The afterglow and lifetime are as follows: At 100℃, it exhibits blue fluorescence under a 380nm UV lamp, and displays a yellow-green afterglow for 15 seconds after the UV lamp is removed, with a lifetime of 1.66 seconds; at 120℃, it exhibits blue fluorescence under a 380nm UV lamp, and displays a yellow-green afterglow for 95 seconds after the UV lamp is removed, with a lifetime of 1.00 seconds; at 140℃, it exhibits blue fluorescence under a 380nm UV lamp, and displays a yellow-green afterglow for 6 seconds after the UV lamp is removed, with a lifetime of 0.66 seconds; at 150℃, it exhibits blue fluorescence under a 380nm UV lamp, and displays a yellow-green afterglow for 1 second after the UV lamp is removed, with a lifetime of 0.38 seconds.

[0077] temperature Phosphorescence wavelength (nm) Phosphorescent afterglow (s) Phosphorescence lifetime (s) 20℃ 494 / 525 36 3.88 40℃ 495 / 525 31 3.45 60℃ 495 / 526 26 3.09 80℃ 495 / 525 20 2.51 100℃ 494 / 525 15 1.66 120℃ 496 / 524 9 1.00 140℃ 495 / 523 4 0.66 150℃ 496 / 526 1 0.38

[0078] Example 8:

[0079] Guest compound 5 obtained in Example 2 was mixed with the host polymer polyvinylpyrrolidone at a ratio of 1:500. The mixture was dissolved in dichloromethane and sonicated for 20 minutes to ensure complete dissolution and homogeneity of both compounds. The mixture was then poured into a mold and baked in an oven at 40°C for 2 hours, followed by baking at 100°C for 12 hours to obtain a polymer-doped luminescent thin film material. The color change of the luminescent material at different temperatures before and after 60 seconds of 380nm ultraviolet light irradiation is shown. (Refer to...) Figure 13 .

[0080] After activation by a 380nm UV lamp for 60 seconds, the polymer film exhibited blue fluorescence under a 380nm UV lamp at 20°C, followed by a long yellow-green afterglow of 22 seconds after the UV lamp was removed, with a lifetime of 2.40 seconds. At 40°C, it showed blue fluorescence under a 380nm UV lamp, followed by a yellow-green afterglow of 19 seconds after the UV lamp was removed, with a lifetime of 2.12 seconds. At 60°C, it showed blue fluorescence under a 380nm UV lamp, followed by a yellow-green afterglow of 16 seconds after the UV lamp was removed, with a lifetime of 1.40 seconds. At 80°C, it showed blue fluorescence under a 380nm UV lamp, followed by a yellow-green afterglow of 12 seconds after the UV lamp was removed. The fluorescence intensity is 1.40 seconds. At 100°C, it exhibits blue fluorescence under a 380nm UV lamp, followed by an 8-second yellow-green afterglow after the UV lamp is removed, resulting in a lifetime of 0.87 seconds. At 120°C, it exhibits blue fluorescence under a 380nm UV lamp, followed by a 6-second yellow-green afterglow after the UV lamp is removed, resulting in a lifetime of 0.63 seconds. At 140°C, it exhibits blue fluorescence under a 380nm UV lamp, followed by a 3-second yellow-green afterglow after the UV lamp is removed, resulting in a lifetime of 0.48 seconds. At 160°C, it exhibits blue fluorescence under a 380nm UV lamp, followed by a 0.5-second yellow-green afterglow after the UV lamp is removed, resulting in a lifetime of 0.09 seconds.

[0081] temperature Phosphorescence wavelength (nm) Phosphorescent afterglow (s) Phosphorescence lifetime (s) 20℃ 491 / 527 22 2.40 40℃ 492 / 527 19 2.12 60℃ 492 / 527 16 1.81 80℃ 492 / 527 12 1.40 100℃ 493 / 528 8 0.87 120℃ 493 / 529 6 0.63 140℃ 492 / 528 3 0.48 160℃ 493 / 528 0.6 0.09

[0082] Example 9:

[0083] Guest compound 6 obtained in Example 2 was mixed with the host polymer polyvinylpyrrolidone at a ratio of 1:500. The mixture was dissolved in dichloromethane and sonicated for 20 minutes to ensure complete dissolution and homogeneity of both compounds. The mixture was then poured into a mold and baked in an oven at 40°C for 2 hours, followed by baking at 100°C for 12 hours to obtain a polymer-doped luminescent thin film material. The color change of the luminescent material at different temperatures before and after 60 seconds of 380nm ultraviolet light irradiation is shown. (Refer to...) Figure 14 .

[0084] After activation by a 380nm UV lamp for 60 seconds, the polymer film exhibited blue fluorescence under a 380nm UV lamp at 20°C, followed by a long yellow-green afterglow of 22 seconds after the UV lamp was removed, with a lifetime of 2.23 seconds. At 40°C, it showed blue fluorescence under a 380nm UV lamp, followed by a yellow-green afterglow of 19 seconds after the UV lamp was removed, with a lifetime of 2.03 seconds. At 60°C, it showed blue fluorescence under a 380nm UV lamp, followed by a yellow-green afterglow of 16 seconds after the UV lamp was removed, with a lifetime of 1.73 seconds. At 80°C, it showed blue fluorescence under a 380nm UV lamp, followed by a yellow-green afterglow of 11 seconds after the UV lamp was removed. The afterglow and lifetime are as follows: At 100℃, it exhibits blue fluorescence under a 380nm UV lamp, and displays a yellow-green afterglow for 7 seconds after the UV lamp is removed, with a lifetime of 0.76 seconds; at 120℃, it exhibits blue fluorescence under a 380nm UV lamp, and displays a yellow-green afterglow for 5 seconds after the UV lamp is removed, with a lifetime of 0.58 seconds; at 140℃, it exhibits blue fluorescence under a 380nm UV lamp, and displays a yellow-green afterglow for 2 seconds after the UV lamp is removed, with a lifetime of 0.33 seconds; at 160℃, it exhibits blue fluorescence under a 380nm UV lamp, and displays a yellow-green afterglow for 0.5 seconds after the UV lamp is removed, with a lifetime of 0.08 seconds.

[0085] temperature Phosphorescence wavelength (nm) Phosphorescent afterglow (s) Phosphorescence lifetime (s) 20℃ 493 / 529 22 2.23 40℃ 494 / 530 19 2.03 60℃ 494 / 531 16 1.73 80℃ 495 / 530 11 1.31 100℃ 494 / 531 7 0.76 120℃ 495 / 532 5 0.58 140℃ 493 / 531 2 0.33 160℃ 493 / 530 0.5 0.08

[0086] Example 10:

[0087] Guest compound 7 obtained in Example 2 was mixed with the host polymer polyvinylpyrrolidone at a ratio of 1:500. The mixture was dissolved in dichloromethane and sonicated for 20 minutes to ensure complete dissolution and homogeneity of both compounds. The mixture was then poured into a mold and baked in an oven at 40°C for 2 hours, followed by baking at 100°C for 12 hours to obtain a polymer-doped luminescent thin film material. The color change of the luminescent material at different temperatures before and after 60 seconds of 380nm ultraviolet light irradiation is shown. (Refer to...) Figure 15 .

[0088] After activation by a 380nm UV lamp for 60 seconds, the polymer film exhibits blue fluorescence under a 380nm UV lamp at 20°C, followed by a long yellow afterglow of 13 seconds after the UV lamp is removed, with a lifetime of 1.38 seconds. At 40°C, it exhibits blue fluorescence under a 380nm UV lamp, followed by a yellow afterglow of 12 seconds after the UV lamp is removed, with a lifetime of 1.36 seconds. At 60°C, it exhibits blue fluorescence under a 380nm UV lamp, followed by a yellow afterglow of 10 seconds after the UV lamp is removed, with a lifetime of 1.26 seconds. At 80°C, it exhibits blue fluorescence under a 380nm UV lamp, followed by a yellow afterglow of 8 seconds after the UV lamp is removed. The afterglow duration is 1.12 seconds. At 100℃, it exhibits blue fluorescence under a 380nm UV lamp, followed by a yellow afterglow for 7 seconds after the UV lamp is removed, with a lifetime of 0.94 seconds. At 120℃, it exhibits blue fluorescence under a 380nm UV lamp, followed by a yellow afterglow for 5 seconds after the UV lamp is removed, with a lifetime of 0.68 seconds. At 140℃, it exhibits blue fluorescence under a 380nm UV lamp, followed by a yellow afterglow for 3 seconds after the UV lamp is removed, with a lifetime of 0.48 seconds. At 160℃, it exhibits blue fluorescence under a 380nm UV lamp, followed by a yellow afterglow for 1 second after the UV lamp is removed, with a lifetime of 0.25 seconds.

[0089] temperature Phosphorescence wavelength (nm) Phosphorescent afterglow (s) Phosphorescence lifetime (s) 20℃ 516 / 556 13 1.38 40℃ 516 / 555 12 1.36 60℃ 517 / 555 10 1.26 80℃ 518 / 556 8 1.12 100℃ 518 / 554 7 0.94 120℃ 518 / 555 5 0.68 140℃ 518 / 554 3 0.48 160℃ 517 / 555 1 0.25

[0090] Example 11:

[0091] Guest compound 8 obtained in Example 2 was mixed with the host polymer polyvinylpyrrolidone at a ratio of 1:500. The mixture was dissolved in dichloromethane and sonicated for 20 minutes to ensure complete dissolution and homogeneity of the guest compound and host polymer. The mixture was then poured into a mold and baked in an oven at 40°C for 2 hours, followed by baking at 100°C for 12 hours to obtain a polymer-doped luminescent thin film material. The color change of the luminescent material at different temperatures before and after 60 seconds of 380nm ultraviolet light irradiation is shown. (Refer to...) Figure 16 .

[0092] After activation by a 380nm UV lamp for 60 seconds, the polymer film exhibited blue fluorescence under a 380nm UV lamp at 20°C, followed by a long yellow afterglow of 13 seconds after the UV lamp was removed, with a lifetime of 1.32 seconds. At 40°C, it showed blue fluorescence under a 380nm UV lamp, followed by a yellow afterglow of 11 seconds after the UV lamp was removed, with a lifetime of 1.21 seconds. At 60°C, it showed blue fluorescence under a 380nm UV lamp, followed by a yellow afterglow of 9 seconds after the UV lamp was removed, with a lifetime of 1.12 seconds. At 80°C, it showed blue fluorescence under a 380nm UV lamp, followed by a yellow afterglow of 8 seconds after the UV lamp was removed. The fluorescence intensity is 1.02 seconds. At 100°C, it exhibits blue fluorescence under a 380nm UV lamp, followed by a 7-second yellow afterglow after the UV lamp is removed, with a lifetime of 0.89 seconds. At 120°C, it exhibits blue fluorescence under a 380nm UV lamp, followed by a 5-second yellow afterglow after the UV lamp is removed, with a lifetime of 0.62 seconds. At 140°C, it exhibits blue fluorescence under a 380nm UV lamp, followed by a 3-second yellow afterglow after the UV lamp is removed, with a lifetime of 0.41 seconds. At 160°C, it exhibits blue fluorescence under a 380nm UV lamp, followed by a 1-second yellow afterglow after the UV lamp is removed, with a lifetime of 0.22 seconds.

[0093] temperature Phosphorescence wavelength (nm) Phosphorescent afterglow (s) Phosphorescence lifetime (s) 20℃ 523 / 561 13 1.32 40℃ 522 / 562 11 1.21 60℃ 523 / 562 9 1.12 80℃ 522 / 562 8 1.02 100℃ 523 / 563 7 0.89 120℃ 522 / 562 5 0.62 140℃ 523 / 562 3 0.41 160℃ 523 / 563 1 0.22

[0094] The above description is merely a preferred embodiment of the present invention. The scope of protection of the present invention is not limited to the above embodiments. All technical solutions falling within the scope of the present invention's concept are within the scope of protection of the present invention. It should be noted that for those skilled in the art, any improvements and modifications made without departing from the principles of the present invention should also be considered within the scope of protection of the present invention.

Claims

1. An organic phosphorescent doped luminescent material, characterized in that: It comprises the following parts by weight: 1-3 parts of the guest compound; 500-1500 parts of the main polymer; The guest compound is a planar rigid organic molecule containing at least three benzene ring structures; The main polymer is polyvinylpyrrolidone; The guest compound is benzo[a]carbazole and its derivatives; The guest compound is at least one selected from 1, 9H-dibenzo[a,c]carbazole, 9-methyl-dibenzo[a,c]carbazole, 9-n-butyl-dibenzo[a,c]carbazole, 9-benzyl-dibenzo[a,c]carbazole, 7H-benzo[c]carbazole, 7-methyl-benzo[c]carbazole, 7H-dibenzo[c,g]carbazole and 7-methyl-dibenzo[c,g]carbazole.

2. The organic phosphorescent doped luminescent material according to claim 1, characterized in that: The number-average molecular weight of the polyvinylpyrrolidone is 50,000 to 400,000.

3. A method for preparing an organic phosphorescent doped luminescent material according to any one of claims 1 to 2, characterized in that: According to the set weight proportions of raw materials, the guest compound and the host polymer are dissolved in dichloromethane and stirred and mixed. After being mixed evenly, the mixture is first treated at a temperature of 30-50℃ for 1-3 hours, and then treated at a temperature of 80-120℃ for 12 hours to obtain the luminescent material.

Images