Benzindole derivatives and light emitting materials prepared therefrom
The benzoindole derivatives doped with PMMA were synthesized by mechanical ball milling under solvent-free conditions, which solved the problems of complex existing synthesis methods and insufficient material stability, and achieved efficient, green synthesis of high-yield benzoindole derivatives with good photoelectric properties and environmental stability, and are suitable for marine pollution prevention and photoelectric equipment.
Patent Information
- Application Number
- CN202410695007.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-05-31
- Publication Date
- 2025-10-17
- Estimated Expiration
- 2044-05-31
AI Technical Summary
The existing synthesis methods of benzindole derivatives are complex, use organic solvents, are costly, and have low yields. It is difficult to achieve efficient synthesis under solvent-free conditions. In addition, the existing materials have insufficient stability and phosphorescence life in harsh environments, which limits their industrial applications and marine anti-pollution effects.
Benzindole derivatives were synthesized under solvent-free conditions at room temperature using mechanical ball milling. By combining a ball mill with a catalyst, the reaction steps were simplified and high-yield benzoindole derivatives were prepared. They were then doped with PMMA to form fluorescent and phosphorescent dual-emission materials. The doping technology was optimized to improve the material's stability and phosphorescence lifetime.
Efficient and green synthesis of high-yield benzindole derivatives at room temperature has been achieved. The material exhibits dual emission of blue-violet fluorescence and strong yellow-green phosphorescence, has a long phosphorescence lifetime and good environmental stability, and is suitable for marine anti-pollution and optoelectronic equipment.
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Figure CN118702615B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the technical field of organic optoelectronic materials, and particularly relates to a kind of benzoindole derivatives and luminescent materials prepared therefrom. BACKGROUND
[0002] With the rapid development of optoelectronic materials technology, especially in the fields of anti-counterfeiting, biological labeling and high-performance optoelectronic devices, there is an increasing demand for new materials with high stability and special optical properties. Phosphorescent materials have shown great potential for application in the above-mentioned fields due to their unique long-lifetime luminescence characteristics. Benzoindole derivatives, as an important class of organic optoelectronic materials, have attracted extensive scientific attention due to their long electron conjugation length and wide absorption band, which exhibit excellent fluorescence and phosphorescence properties. These substances not only have important applications in the field of optoelectronics, but also have potential application value in the fields of medicine and biological labeling due to their high biological activity.
[0003] However, the existing synthesis methods of benzoindole derivatives usually involve complex chemical reaction conditions, such as high temperature, the use of organic solvents and multi-step reactions, which not only increase the production cost, but also cause great pressure on the environment. In addition, these methods often have difficulty in controlling the purity and yield of the product, which limits the feasibility of benzoindole derivatives in industrial-scale applications. The use of solvents in traditional methods is particularly prominent, as they often involve toxic solvents, increasing the risk of operation and causing continuous harm to the environment. Although the mechanical chemical synthesis method provides a potential alternative, it still faces a great technical challenge in achieving high efficiency and high selectivity under solvent-free conditions in practical applications.
[0004] In addition, although the two-component doped system of benzoindole derivatives and polymethyl methacrylate (PMMA) has shown excellent optoelectronic properties, such as room-temperature dual-emission characteristics, there is still a major problem in current technology in how to further improve the phosphorescence lifetime and environmental stability of these materials, especially in harsh environments such as the ocean. Although existing multi-component doped materials can provide certain performance improvement, there is still room for improvement in terms of optoelectronic performance, biocompatibility and environmental friendliness, especially in terms of improving phosphorescence efficiency and extending phosphorescence lifetime.
[0005] In summary, there is an urgent need to develop a simple, green and efficient synthesis method that can not only synthesize high-yield benzoindole derivatives at room temperature without the use of organic solvents, but also significantly improve the optoelectronic performance and environmental stability of phosphorescent materials through optimized doping technology. This new synthesis strategy and material design will provide significant technical progress in the field of optoelectronic materials, especially in the application of marine antifouling and optoelectronic devices. Summary of the Invention
[0006] In order to achieve the above-mentioned purpose of the invention, in view of the above-mentioned technical problems,
[0007] The present invention provides a benzindole derivative for use as a fluorescent and phosphorescent dual-emission luminescent material, wherein the benzindole derivative comprises the following categories:
[0008] Benzindole derivatives Class A;
[0009] Benzindole derivatives Class B;
[0010] Benzindole derivatives Class C;
[0011] Benzindole derivatives Class D;
[0012] Benzindole derivatives Class E.
[0013] Preferably, the benzindole derivatives A include compounds 1-6, and the structural formulas of the compounds 1-6 are as follows:
[0014]
[0015] The benzindole derivatives B include compounds 7-12, and the structural formula of the compound 7-12 is as follows:
[0016]
[0017] The benzindole derivatives C include compounds 13-27, and the structural formulas of the compounds 13-27 are as follows:
[0018]
[0019] The benzindole derivatives D include compounds 28-37, and the structural formulas of the compounds 28-37 are as follows:
[0020]
[0021] The benzindole derivatives E include compounds 38-39, and the structural formulas of the compounds 38-39 are as follows:
[0022]
[0023] Preferably, the reaction formula of the benzindole derivative type A is:
[0024]
[0025] The reaction formula of the benzindole derivative B is:
[0026]
[0027] The reaction formula of the benzindole derivative C is:
[0028]
[0029] The reaction formula of the benzindole derivative D is:
[0030]
[0031] The reaction formula of the benzindole derivative E is:
[0032]
[0033] Preferably, the preparation method of the benzindole derivative is as follows:
[0034] The preparation method of the benzindole derivative A is as follows:
[0035] Compound 1-naphthalene hydrazine hydrochloride and 6 different substituents of phenylpropyl ketone are added to the ball mill jar in a molar ratio of 1:1.1, then oxalic acid, dimethyl urea and acetic acid are added to the ball mill jar in a molar ratio of 1:3.5:1.5 equivalent to 1-naphthalene hydrazine hydrochloride, and finally acetic acid is added as a catalyst in a mass ratio of 0.1 ul / mg to 1-naphthalene hydrazine hydrochloride;
[0036] After the ball mill jar is covered, it is fixed in a planetary ball mill, and the reaction is carried out at room temperature, in an air atmosphere, at 30 Hz for 2 h;
[0037] After the reaction is completed, the reaction mixture is cooled to room temperature, then the product is transferred to a tomato-shaped bottle, dissolved with an organic solvent, then the organic solvent is evaporated under reduced pressure, and white solid is obtained by silica gel column chromatography to obtain compounds of structural formula 1-6.
[0038] The preparation method of the benzindole derivative B is as follows:
[0039] Compound 2-naphthalene hydrazine hydrochloride and 6 different substituents of phenylpropyl ketone are added to the ball mill jar in a molar ratio of 1:1.1, then oxalic acid, dimethyl urea and acetic acid are added to the ball mill jar in a molar ratio of 1:3.5:1.5 equivalent to 2-naphthalene hydrazine hydrochloride, and finally acetic acid is added as a catalyst in a mass ratio of 0.1 ul / mg to 2-naphthalene hydrazine hydrochloride;
[0040] After the ball mill jar is covered, it is fixed in a planetary ball mill, and the reaction is carried out at room temperature, in an air atmosphere, at 30 Hz for 2 h;
[0041] After the reaction is completed, the reaction mixture is cooled to room temperature, then the product is transferred to a tomato-shaped bottle, dissolved with an organic solvent, then the organic solvent is evaporated under reduced pressure, and white solid is obtained by silica gel column chromatography to obtain compounds of structural formula 1-6.
[0042] The preparation method of the benzindole derivative C is as follows:
[0043] The compound 2-naphthalene hydrazine hydrochloride and 15 different substituted phenylpropanone are added into a ball mill jar in a molar ratio of 1:1.1, then oxalic acid, dimethyl urea and acetic acid are added into the ball mill jar in a molar ratio of 1:3.5:1.5 equivalent of 2-naphthalene hydrazine hydrochloride, and finally acetic acid is added as a catalyst in a mass ratio of 0.1 ul / mg of 2-naphthalene hydrazine hydrochloride;
[0044] After the ball mill jar is covered, it is fixed in a planetary ball mill, and the reaction is carried out at room temperature, in an air atmosphere, at 30 Hz for 2 h.
[0045] After the reaction is completed, the reaction mixture is cooled to room temperature, then the product is transferred into a tomato-shaped bottle, dissolved with an organic solvent, and then the organic solvent is evaporated under reduced pressure to obtain a white solid through silica gel column chromatography to obtain the compound with the structural formula 13-27.
[0046] The preparation method of the benzindole derivative D is as follows:
[0047] The compound 6 is dissolved in 15 ml of DMF in a molar ratio of 1:1.5 with substituted phenylboronic acid, and the reaction is carried out at 85 DEG C for 12 hours under N2 atmosphere to obtain the reaction product.
[0048] Then, the reaction product 0.5 mmol is poured into 150 ml of water, extracted with ethyl acetate for three times, then the organic phase is dried with anhydrous sodium sulfate, and then the organic solvent is evaporated under reduced pressure to obtain the compound with the structural formula 28-37 through column chromatography.
[0049] The preparation method of the benzindole derivative E is as follows:
[0050] The compound 6 is dissolved in 15 ml of toluene in a molar ratio of 1:1.5 with carbazole and diphenylamine (as shown below), and the reaction is carried out at 105 DEG C for 12 hours under N2 atmosphere to obtain the reaction product.
[0051] Then, the reaction product 0.5 mmol is poured into 150 ml of water, extracted with ethyl acetate for three times, then the organic phase is dried with anhydrous sodium sulfate, and then the organic solvent is evaporated under reduced pressure to obtain the compound with the structural formula 38-39 through column chromatography.
[0052] The application further provides a fluorescent and phosphorescent dual-emission light-emitting material, and the preparation raw material of the light-emitting material comprises a benzindole derivative and polymethyl methacrylate (PMMA), and the benzindole derivative is prepared by the above preparation method.
[0053] Preferably, the mass mixing ratio of the benzindole derivative and PMMA is 1:100.
[0054] Preferably, the preparation method of the light-emitting material is as follows:
[0055] The benzindole derivative and PMMA are respectively dissolved in ethyl acetate at a mass ratio of 1:100, and then ultrasonic treatment is performed in an ultrasonic instrument;
[0056] The PMMA solution is added dropwise into the benzindole derivative solution to obtain a mixture, and then ultrasonic treatment is performed in an ultrasonic instrument to make it uniformly dissolved;
[0057] The well-mixed two-component solution is slowly poured into a mold, and after drying, a light-emitting material is obtained.
[0058] Preferably, the ultrasonic treatment time is 10 min.
[0059] Preferably, the drying temperature is 50 DEG C, and the time is 2 hours.
[0060] The technical scheme provided by the present application has the following beneficial effects:
[0061] The present application synthesizes a new type of benzindole derivative in a simple, green and efficient way, and adopts a low-cost mechanical force ball milling method to synthesize benzindole derivative with high yield in one step at room temperature, in a solvent-free and air atmosphere.
[0062] The benzindole derivative synthesized by the present application exhibits blue-purple fluorescence and strong yellow-green phosphorescence double emission. The present application can prepare a thin film material with a long phosphorescence lifetime, and the material has stability in seawater and good application prospect in the ocean.
[0063] The series of benzindole derivatives synthesized by the present application have certain bactericidal effect, and can be used in marine antifouling and corrosion prevention. BRIEF DESCRIPTION OF DRAWINGS
[0064] Figure 1 The luminescent color changes of the guest compounds 1-6 and the host PMMA doped material before and after ultraviolet light irradiation are provided for the embodiments of the present application.
[0065] Figure 2 The luminescent color changes of the guest compounds 34-35 and the host PMMA doped material before and after ultraviolet light irradiation are provided for the embodiments of the present application.
[0066] Figure 3 The luminescent color changes of the guest compounds 36-37 and the host PMMA doped material before and after ultraviolet light irradiation are provided for the embodiments of the present application.
[0067] Figure 4Phosphorescence emission diagram of guest compounds 1-6 and host PMMA doped material provided by the embodiment of the present application;
[0068] Figure 5 Phosphorescence emission diagram of guest compounds 34-35 and host PMMA doped material provided by the embodiment of the present application;
[0069] Figure 6 Phosphorescence emission diagram of guest compounds 36-37 and host PMMA doped material provided by the embodiment of the present application;
[0070] Figure 7 Phosphorescence decay curve of guest compounds 4-6 and host PMMA doped material provided by the embodiment of the present application, the phosphorescence lifetime of F-Bd / PMMA doped film is up to 1.65 s;
[0071] Figure 8 Phosphorescence decay curve of literature reported Bd / PMMA doped film, the phosphorescence lifetime of literature reported Bd / PMMA film is only 0.29 s;
[0072] Figure 9 Fluorescence emission diagram of guest compounds 1-6 and host PMMA doped material provided by the embodiment of the present application;
[0073] Figure 10 Fluorescence decay curve of guest compounds 1-6 and host PMMA doped material provided by the embodiment of the present application;
[0074] Figure 11 Bacteriostatic effect diagram of guest compounds 2, 4-6 on escherichia coli provided by the embodiment of the present application;
[0075] Figure 12 Nuclear magnetic resonance hydrogen spectrum of guest compound 1 provided by the embodiment of the present application;
[0076] Figure 13 Nuclear magnetic resonance carbon spectrum of guest compound 1 provided by the embodiment of the present application;
[0077] Figure 14 Nuclear magnetic resonance hydrogen spectrum of guest compound 2 provided by the embodiment of the present application;
[0078] Figure 15 Nuclear magnetic resonance carbon spectrum of guest compound 2 provided by the embodiment of the present application;
[0079] Figure 16 Nuclear magnetic resonance hydrogen spectrum of guest compound 3 provided by the embodiment of the present application;
[0080] Figure 17 Nuclear magnetic resonance carbon spectrum of guest compound 3 provided by the embodiment of the present application;
[0081] Figure 18 NMR of the object compound 8 provided by the embodiment of the present application;
[0082] Figure 19 NMR of the object compound 13 provided by the embodiment of the present application;
[0083] Figure 20 Single crystal structure diagram of the object compound 13 provided by the embodiment of the present application;
[0084] Figure 21 NMR of the object compound 33 provided by the embodiment of the present application;
[0085] Figure 22 NMR of the object compound 35 provided by the embodiment of the present application; DETAILED DESCRIPTION
[0086] In order to make the objects, technical solutions and advantages of the present application clearer, the present application will be further described in detail below in combination with embodiments. Of course, the specific embodiments described herein are only used to explain the present application, and are not used to limit the present application.
[0087] Embodiment 1
[0088] A class of benzindole derivatives A, the preparation method is as follows:
[0089] Compound 1-naphthalene hydrazine hydrochloride is added into a ball mill tank with benzaldehyde with six different substituents (as shown below) at a molar ratio of 1:1.1,
[0090]
[0091] Then oxalic acid, dimethyl urea and acetic acid are added into the ball mill tank at a molar ratio of 1:3.5:1.5 with respect to 1-naphthalene hydrazine hydrochloride, and the acetic acid is used as a catalyst at a mass ratio of 0.1 ul / mg with respect to 1-naphthalene hydrazine hydrochloride;
[0092] After the ball mill tank is covered, it is fixed to a planetary ball mill, and the reaction is carried out at room temperature, in an air atmosphere, at 30 Hz for 2 h;
[0093] After the reaction is completed, the reaction mixture is cooled to room temperature, then the product is transferred into a tomato-shaped bottle, dissolved with an organic solvent, and then the organic solvent is evaporated under reduced pressure to obtain a white solid through silica gel column chromatography to obtain compounds of structural formula 1-6.
[0094] Embodiment 2
[0095] The preparation method of the benzindole derivative B is as follows:
[0096] Compound 2-naphthalene hydrazine hydrochloride was added into the ball mill jar with 6 different substituent groups (as shown below) of phenylpropyl ketone at a molar ratio of 1:1.1, respectively,
[0097]
[0098] Then oxalic acid, dimethyl urea were added into the ball mill jar at a molar ratio of 1:3.5:1.5 equivalent to 2-naphthalene hydrazine hydrochloride, and finally acetic acid was added as a catalyst at a mass ratio of 0.1 ul / mg to 2-naphthalene hydrazine hydrochloride;
[0099] After the ball mill jar was covered, it was fixed in the planetary ball mill, and reacted at room temperature, air atmosphere, 30 Hz for 2 h;
[0100] After the reaction was completed, the reaction mixture was cooled to room temperature, and then the product was transferred into a tomato-shaped bottle, dissolved with an organic solvent, and then the organic solvent was evaporated under reduced pressure to obtain a white solid by silica gel column chromatography to obtain compounds with structural formula 7-12.
[0101] Example 3
[0102] The preparation method of the benzindole derivative C is as follows:
[0103] Compound 2-naphthalene hydrazine hydrochloride was added into the ball mill jar with 15 different substituent groups (as shown below) of phenylpropyl ketone at a molar ratio of 1:1.1, respectively, and then oxalic acid, dimethyl urea were added into the ball mill jar at a molar ratio of 1:3.5:1.5 equivalent to 2-naphthalene hydrazine hydrochloride, and finally acetic acid was added as a catalyst at a mass ratio of 0.1 ul / mg to 2-naphthalene hydrazine hydrochloride;
[0104]
[0105] After the ball mill jar was covered, it was fixed in the planetary ball mill, and reacted at room temperature, air atmosphere, 30 Hz for 2 h;
[0106] After the reaction was completed, the reaction mixture was cooled to room temperature, and then the product was transferred into a tomato-shaped bottle, dissolved with an organic solvent, and then the organic solvent was evaporated under reduced pressure to obtain a white solid by silica gel column chromatography to obtain compounds with structural formula 13-27.
[0107] Example 4
[0108] The preparation method of the benzindole derivative D is as follows:
[0109] Compound 6 was dissolved in 15 ml of DMF at 0.5 mmol, and then reacted with substituted phenylboronic acid (as shown below) at a molar ratio of 1:1.5 under N2 atmosphere at 85 ℃ for 12 hours to obtain the reaction product;
[0110]
[0111] The reaction product 0.5 mmol is then poured into 150 ml of water, extracted with ethyl acetate three times, and the organic phase is dried with anhydrous sodium sulfate, and then the organic solvent is evaporated under reduced pressure to obtain compounds of structural formula 28-37 by column chromatography.
[0112] Example 5
[0113] The preparation method of the benzindole derivative E is as follows:
[0114] Compound 6 is dissolved with carbazole, diphenylamine (as shown below) at a molar ratio of 1:1.5, 0.5 mmol in 15 ml of toluene, and the reaction product is obtained by reacting at 85°C for 12 hours under N2 atmosphere.
[0115]
[0116] The reaction product 0.5 mmol is then poured into 150 ml of water, extracted with ethyl acetate three times, and the organic phase is dried with anhydrous sodium sulfate, and then the organic solvent is evaporated under reduced pressure to obtain compounds of structural formula 28-37 by column chromatography.
[0117] Example 6
[0118] A fluorescent and phosphorescent dual-emission light-emitting material is prepared by the following method:
[0119] The benzindole derivative A prepared in Example 1 and PMMA are respectively dissolved in ethyl acetate at a mass ratio of 1:100, and then ultrasonic treatment is performed in an ultrasonic instrument for 10 min.
[0120] The PMMA solution is added dropwise to the benzindole derivative A solution to obtain a mixture, and the mass mixing ratio of the benzindole derivative to PMMA is 1:100, and then ultrasonic treatment is performed to make them uniformly dissolved in the ultrasonic instrument.
[0121] The well-mixed two-component solution is slowly poured into a mold, and after drying at a temperature of 50°C for 2 hours, a light-emitting material is obtained.
[0122] Example 7
[0123] A fluorescent and phosphorescent dual-emission light-emitting material is prepared by the following method:
[0124] The benzindole derivative B prepared in Example 2 and PMMA are respectively dissolved in ethyl acetate at a mass ratio of 1:100, and then ultrasonic treatment is performed in an ultrasonic instrument for 10 min.
[0125] The PMMA solution is added dropwise into the solution of the benzindole derivative B to obtain a mixture, the mass mixing ratio of the benzindole derivative and PMMA is 1:100, and then the mixture is ultrasonically treated in an ultrasonic instrument to make it uniformly dissolved;
[0126] The well-mixed two-component solution is slowly poured into a mold, and a luminescent material is obtained after drying, the drying temperature is 50°C, and the drying time is 2 hours.
[0127] Example 8
[0128] A fluorescent and phosphorescent dual-emission luminescent material is prepared by the following method:
[0129] The benzindole derivative C prepared in Example 3 and PMMA are respectively dissolved in ethyl acetate, the mass ratio is 1:100, and then ultrasonic treatment is performed in an ultrasonic instrument, the ultrasonic treatment time is 10 min;
[0130] The PMMA solution is added dropwise into the solution of the benzindole derivative C to obtain a mixture, the mass mixing ratio of the benzindole derivative and PMMA is 1:100, and then the mixture is ultrasonically treated in an ultrasonic instrument to make it uniformly dissolved;
[0131] The well-mixed two-component solution is slowly poured into a mold, and a luminescent material is obtained after drying, the drying temperature is 50°C, and the drying time is 2 hours.
[0132] Example 9
[0133] A fluorescent and phosphorescent dual-emission luminescent material is prepared by the following method:
[0134] The benzindole derivative D prepared in Example 4 and PMMA are respectively dissolved in ethyl acetate, the mass ratio is 1:100, and then ultrasonic treatment is performed in an ultrasonic instrument, the ultrasonic treatment time is 10 min;
[0135] The PMMA solution is added dropwise into the solution of the benzindole derivative D to obtain a mixture, the mass mixing ratio of the benzindole derivative and PMMA is 1:100, and then the mixture is ultrasonically treated in an ultrasonic instrument to make it uniformly dissolved;
[0136] The well-mixed two-component solution is slowly poured into a mold, and a luminescent material is obtained after drying, the drying temperature is 50°C, and the drying time is 2 hours.
[0137] Example 10
[0138] A fluorescent and phosphorescent dual-emission luminescent material is prepared by the following method:
[0139] The benzindole derivative E prepared from Example 5 and PMMA are respectively dissolved in ethyl acetate with a mass ratio of 1:100, and then ultrasonic treatment is carried out in an ultrasonic instrument, and the ultrasonic treatment time is 10 min.
[0140] The PMMA solution is added dropwise into the benzindole derivative E solution to obtain a mixture, and the mass mixing ratio of the benzindole derivative and PMMA is 1:100, and then ultrasonic treatment is carried out in an ultrasonic instrument to make them uniformly dissolved.
[0141] The well-mixed two-component solution is slowly poured into a mold, and after drying, a luminescent material is obtained, and the drying temperature is 50 DEG C, and the time is 2 hours.
[0142] Figures 1 to 3 It is proved that the luminescent material has blue-violet fluorescence under ultraviolet lamp irradiation, and has green phosphorescence after the ultraviolet lamp is turned off.
[0143] Figure 4 、 5 , 6, 9 are phosphorescence emission spectrum diagrams of the luminescent materials, and the emission wavelengths of the materials are all about 500-520 nm, which is a green light emission range.
[0144] Through the above data, it can be proved that other luminescent materials prepared by the present application also have such effects.
[0145] Figure 7 is a phosphorescence lifetime decay curve of a benzindole derivative and PMMA doped thin film synthesized by the present application, Figure 8 is a phosphorescence lifetime decay curve of another benzindole and PMMA doped thin film reported in the literature. Figure 7 With Figure 8 By comparison, it can be seen that the benzindole derivative of the present application not only has a simple synthesis process, but also has a longer phosphorescence lifetime of the thin film prepared by doping with PMMA, which is more than five times the phosphorescence lifetime of the reported Bd / PMMA thin film. Figure 8 Reference from Intrinsic persistent room temperature phosphorescence derived from 1H -benzo[ f ]indole itself as a guest.
[0146] Figure 10 is the fluorescence lifetime of the doped material.
[0147] Figure 11 It is illustrated that the benzindole derivative synthesized by the new method has antibacterial properties, and can be used in marine antifouling.
[0148] Figures 12-22Respectively are hydrogen spectrum, carbon spectrum, single crystal chart of compound. Prove the structure of compound synthesized by new method, and purity.
[0149] It can be proved by the above data that other benzindole derivatives and light emitting materials prepared by the application also have such effects.
[0150] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims
1. A benzindole derivative for use as a fluorescent and phosphorescent dual-emission luminescent material, characterized in that: The benzindole derivatives include the following categories: Benzindole derivatives Class A; Benzindole derivatives Class D; The benzindole derivatives A include compounds 3 and 6, and the structural formula is as follows: The benzindole derivatives D include the following compounds, and the structural formula of the compounds is as follows: 。 2. A method for preparing the benzindole derivative according to claim 1, characterized in that: The preparation method of the benzindole derivative type A is as follows: The compound 1-naphthylhydrazine hydrochloride and phenylacetone with different substituents were added to a ball mill at a molar ratio of 1:1.
1. Then, oxalic acid and dimethyl urea were added to the ball mill at a molar ratio of 1:3.5:1.5 equivalents to 1-naphthylhydrazine hydrochloride. Finally, acetic acid was added as a catalyst at a mass ratio of 0.1 ul / mg to 1-naphthylhydrazine hydrochloride. After the ball mill jar is covered, it is fixed in a planetary ball mill and reacted at room temperature, air atmosphere, and 30 Hz for 2 h; After the reaction is completed, the reaction mixture is cooled to room temperature, and the product is then transferred to an eggplant-shaped flask and dissolved with an organic solvent. The organic solvent is then evaporated under reduced pressure and a white solid is obtained by silica gel column chromatography to obtain a benzindole derivative A compound; The preparation method of the benzindole derivative D is as follows: Compound 6 and substituted phenylboronic acid were dissolved in 15 mL of DMF at a molar equivalent ratio of 1:1.5, and the reaction was carried out at 85 °C for 12 hours under a nitrogen atmosphere to obtain the reactant. Then, 0.5 mmol of the reactant was poured into 150 ml of water and extracted three times with ethyl acetate. The organic phase was then dried over anhydrous sodium sulfate. The organic solvent was then evaporated under reduced pressure and the benzindole derivative D compound was obtained by column chromatography.
3. A fluorescent and phosphorescent dual-emission luminescent material, characterized in that: The raw materials for preparing the luminescent material include benzindole derivatives and polymethyl methacrylate (PMMA), and the benzindole derivatives are prepared by the preparation method according to claim 2.
4. The luminescent material according to claim 3, characterized in that The mass mixing ratio of the benzindole derivative to PMMA is 1:
100.
5. The luminescent material according to claim 3, characterized in that The preparation method of the luminescent material is as follows: The benzindole derivative and PMMA were dissolved in ethyl acetate at a mass ratio of 1:100, and then sonicated in an ultrasonic instrument; The PMMA solution is added dropwise to the benzindole derivative solution to obtain a mixture, which is then sonicated in an ultrasonic instrument to uniformly dissolve the mixture. The fully mixed two-component solution is slowly poured into a mold and dried to obtain a luminescent material.
6. The luminescent material according to claim 5, characterized in that The ultrasonic treatment time is 10 min.
7. The luminescent material according to claim 5, characterized in that The drying temperature was 50°C and the drying time was 2 hours.