Solid-state photoluminescence-enhanced material, preparation method and application thereof

Abstract

The application relates to a solid-state photoluminescence-enhancing material, a preparation method and application thereof in the field of photoluminescence enhancement, and belongs to the technical field of solid-state photoluminescence-enhancing materials. Anthracene groups with high luminescence are taken as cores, and carbazole groups and triphenylamine groups are taken as side groups, so that the molecules have an ordered stacking structure. Since the monodisperse molecular monomers have high luminescence, the [4+4] photodimerization of anthracene is first caused in the solid state through ultraviolet irradiation; then, since the reaction degree is low, the [4+4] photodimerization of anthracene is not caused any more, and the energy is used for the absorption of the ground state electrons of the monomers; and macroscopically, the fluorescence is enhanced. The application skillfully avoids the low luminescence of the dimer which is seriously destroyed in conjugation, and since the [4+4] photodimerization reaction of anthracene has the characteristics, the dimer can quickly and reversibly return to the monomer state under heating conditions, so that the application has important significance for the field of solid-state photoluminescence enhancement.

Description

Technical Field

[0001] This invention belongs to the field of solid-state photoluminescence enhancement technology, specifically relating to a solid-state photoluminescence enhancement material, its preparation method, and its application in the field of photoluminescence enhancement. Background Technology

[0002] In the aggregated state, the fluorescence properties of molecular systems are always influenced by the molecular packing pattern. Therefore, studying the relationship between molecular arrangement and fluorescence properties at the molecular level is of great significance for obtaining ideal solid-state organic light-emitting materials. In solution, molecules are in a highly dispersed state, so generally, ordinary organic fluorescent materials can undergo reversible structural changes between two photoisomers in solution, thus exhibiting enhanced fluorescence optical properties under light stimulation. However, in solids, the closed molecular packing restricts their structural transformation, leading to a lack of practicality or negative impacts on real-world applications. To address this issue, fluorescence enhancement has been introduced into various porous phases to mitigate the effects of dense molecular packing, achieving sufficient conformational freedom in space. Nevertheless, achieving photoisomerization in solid-state single-component molecular systems remains very difficult.

[0003] Solid-state topological chemistry reactions can be carried out without solvents or catalysts and do not require product separation or purification, attracting widespread attention from researchers. Solid-state topological chemistry reactions often involve the [4+4] photodimerization of anthracene. Under solid-state conditions, the [4+4] photodimerization of anthracene involves strict regioselectivity and stereoselectivity, with the primary condition being highly ordered molecular stacking. Generally, the dimer formed by the [4+4] photodimerization of anthracene brings about significant structural changes in the molecules. Simultaneously, due to the steric hindrance caused by the highly ordered stacking, the reaction macroscopically manifests as large geometric changes in the crystal, exhibiting various mechanical motion properties such as bending, rotation, and coiling. Furthermore, the molecules retain their new shape even after exciton de-excitation. However, the newly formed dimer breaks the original π-conjugation of the monomer, often severely disrupting the luminescence of the product, thus rarely showing fluorescence enhancement.

[0004] Therefore, developing a material that can still exhibit reversible fluorescence enhancement after [4+4] photodimerization of anthracene in the solid state is of great significance to the field of fluorescence enhancement. Summary of the Invention

[0005] The purpose of this invention is to provide a solid-state photoluminescence enhancement material, its preparation method, and its application in the field of photoluminescence enhancement.

[0006] The solid-state photoluminescent enhancement materials prepared by this invention have excellent reversibility and are named 1-(4-(9-carbazolyl)phenyl)-2-(9-anthrayl)acetylene (Formula 1), 1-(4-(9-carbazolyl)phenyl)-2-(9-anthrayl)ethylene (Formula 2), and 1-(4-(diphenylamino)phenyl)-2-(9-anthrayl)ethylene (Formula 3), respectively, and their structural formulas are shown below:

[0007]

[0008] This invention also provides a method for preparing the above-mentioned solid-state photoluminescence enhancement material, and all raw materials can be purchased commercially.

[0009] The preparation steps of compound 1 are as follows:

[0010] (1) 9-(4-bromophenyl)carbazole was mixed with trimethylethynylsilane, catalyst and CuI in a solvent to carry out the first coupling reaction. The product was extracted with water and dichloromethane, purified by column chromatography of the lower organic phase solution, and pure petroleum ether was used as the developing solvent to obtain 9-((4-trimethylsilaneethynyl)phenyl)carbazole.

[0011] (2) Dissolve 9-((4-trimethylsilylethynyl)phenyl)carbazole in dichloromethane, add tetrabutylammonium fluoride to remove the trimethylsilyl group after deprotection, concentrate the product and extract it with water and ethyl acetate, take the upper organic phase for rotary evaporation and cooling to obtain 9-p-ethynylphenylcarbazole.

[0012] (3) 9-p-acetylenylphenylcarbazole, 9-bromoanthracene, catalyst, and CuI were mixed in a solvent and subjected to a second coupling reaction. The product was extracted with water and dichloromethane, and purified by column chromatography of the lower organic phase solution. Petroleum ether:dichloromethane volume ratio = 3-5:1 was used as the developing solvent to obtain 1-(4-(9-carbazolyl)phenyl)-2-(9-anthrayl)acetylene white solid powder.

[0013] Preferably, in step (1), the molar ratio of 9-(4-bromophenyl)carbazole to trimethylethynylsilane, catalyst, and CuI is 1:1 to 1.2:0.1:0.1, and the solvent is a mixture of ultra-dry tetrahydrofuran and diisopropylamine in a volume ratio of 1 to 3:1.

[0014] Preferably, in step (2), the molar ratio of 9-((4-trimethylsilylethynyl)phenyl)carbazole to tetrabutylammonium fluoride is 1:3-5;

[0015] Preferably, in step (3), the molar ratio of 9-p-acetylenylphenylcarbazole to 9-bromoanthracene, catalyst, and CuI is 1:1 to 1.2:0.1:0.1, and the solvent is a mixture of ultra-dry tetrahydrofuran and diisopropylamine in a volume ratio of 1 to 3:1.

[0016] Preferably, the reaction temperature of the first coix seed coupling reaction is 70–90°C, and the reaction time is 30–40 hours;

[0017] Preferably, the reaction temperature of the second coix seed coupling reaction is 100–120°C, and the reaction time is 15–25 hours.

[0018] Preferably, the catalysts for the first and second coix seed coupling reactions are one or two of bis(triphenylphosphine)palladium dichloride and 1,1-bis(dibenzylphosphine)ferrocene palladium dichloride dichloromethane complex.

[0019] The preparation steps of compound 2 are as follows:

[0020] (1) Carbazole, 4-bromostyrene, sodium tert-butoxide, tridibenzylacetone dipalladium, and tritert-tert-butylphosphine tetrafluoroborate were mixed in a solvent and subjected to a first reflux reaction. The reflux product was extracted with water and dichloromethane, and the lower organic phase solution was purified by column chromatography. Pure petroleum ether was used as the developing solvent to obtain 1-(4-(9-carbazole)phenyl)ethylene white solid powder.

[0021] (2) 1-(4-(9-carbazolyl)phenyl)ethylene, 9-bromoanthracene, sodium carbonate, and palladium acetate were mixed in a solvent and subjected to a second reflux reaction. The reflux product was extracted with water and dichloromethane, and the lower organic phase solution was purified by column chromatography. Petroleum ether:dichloromethane volume ratio = 3~5:1 was used as the developing solvent to obtain 1-(4-(9-carbazolyl)phenyl)-2-(9-anthrayl)ethylene yellow powder.

[0022] Preferably, in step (1), the molar ratio of carbazole, 4-bromostyrene, sodium tert-butoxide, tridibenzylacetone dipalladium, and tritert-tert-butylphosphine tetrafluoroborate is 1.2–1.4:1:0.05:0.05, and the solvent is toluene;

[0023] Preferably, in step (2), the molar ratio of 1-(4-(9-carbazolyl)phenyl)ethylene, 9-bromoanthracene, sodium carbonate, and palladium acetate is 3.7:3.9:5.6:0.2-0.3, and the solvent is N,N-dimethylformamide;

[0024] Preferably, in step (1), the reaction temperature of the first reflux reaction is 80-100°C, and the reaction time is 3-6 hours;

[0025] Preferably, in step (2), the reaction temperature of the second reflux reaction is 100-120°C, and the reaction time is 3-6 hours.

[0026] The preparation steps of compound formula 3 are as follows:

[0027] (1) Diphenylamine, 4-bromostyrene, sodium tert-butoxide, tridibenzylacetone dipalladium, and tritert-tert-butylphosphine tetrafluoroborate were mixed in a solvent and subjected to a third reflux reaction. The reflux product was extracted with water and dichloromethane, and the lower organic phase solution was purified by column chromatography with petroleum ether as the developing solvent to obtain 1-(4-(diphenylamino)phenyl)ethylene white solid powder.

[0028] (2) 1-(4-(diphenylamino)phenyl)ethylene, 9-bromoanthracene, sodium carbonate, and palladium acetate were mixed in a solvent and subjected to a fourth reflux reaction. The reflux product was extracted with water and dichloromethane, and the lower organic phase solution was purified by column chromatography. Petroleum ether:dichloromethane volume ratio = 3-5:1 was used as the developing solvent to obtain 1-(4-(diphenylamino)phenyl)-2-(9-anthrayl)ethylene green powder.

[0029] Preferably, in step (1), the molar ratio of diphenylamine, 4-bromostyrene, sodium tert-butoxide, tridibenzylacetone dipalladium, and tritert-tert-butylphosphine tetrafluoroborate is 1.2–1.4:1:0.05:0.05, and the solvent is toluene;

[0030] Preferably, in step (2), the molar ratio of 1-(4-(diphenylamino)phenyl)ethylene, 9-bromoanthracene, sodium carbonate, and palladium acetate is 3.7:3.9:5.6:0.2-0.3, and the solvent is N,N-dimethylformamide;

[0031] Preferably, in step (1), the reaction temperature of the third reflux reaction is 20-40°C, and the reaction time is 0.5-2.0 hours;

[0032] Preferably, in step (2), the reaction temperature of the fourth reflux reaction is 100-120°C and the reaction time is 3-6 hours.

[0033] This invention uses anthracene, which inherently possesses high luminescence, as the core, and introduces carbazole and triphenylamine groups as side groups to ensure an ordered molecular stacking structure. Since the monodisperse monomers themselves have high luminescence, ultraviolet irradiation in the solid state first induces [4+4] photodimerization of anthracene. Subsequently, due to the low degree of reaction, the material ceases [4+4] photodimerization of anthracene and instead uses energy for the absorption of ground-state electrons in the monomer, macroscopically manifesting as enhanced fluorescence. This invention cleverly avoids the low luminescence of the severely disrupted conjugated dimer, and due to the characteristics of the [4+4] photodimerization reaction of anthracene, the dimer can rapidly and reversibly return to the monomer state under heating conditions, which is of great significance in the field of solid-state photoluminescence enhancement. Attached Figure Description

[0034] Figure 1a )and Figure 1bExample 1: The photoluminescent enhancement material prepared in this example is in powder form. Before irradiation with a 365nm ultraviolet lamp ( Figure 1a ))back( Figure 1b Photographs showing the changes in fluorescence intensity.

[0035] Figure 2a )and Figure 2b Example 2: The photoluminescent enhancement material prepared in this example is in powder form. Before irradiation with a 365nm ultraviolet lamp ( Figure 2a ))back( Figure 2b Photographs showing the changes in fluorescence intensity.

[0036] Figure 3a )and Figure 3b Example 3: The photoluminescent enhancement material prepared in the form of powder was exposed to a 365nm ultraviolet lamp before irradiation. Figure 3a ))back( Figure 3b Photographs showing the changes in fluorescence intensity.

[0037] Figure 4 Emission spectra of the photoluminescent enhancement material prepared in Example 1 after UV irradiation for different times by crystals obtained by vapor deposition.

[0038] Figure 5a )and Figure 5b Example 1: Photoluminescent enhancement material prepared before UV irradiation ( Figure 5a )back( Figure 5b The crystal structure diagram of anthracene is shown. This illustrates that after ultraviolet irradiation, the crystal described in Example 1 reacts from monomer to form a dimer, indicating that the [4+4] photodimerization reaction of anthracene occurred.

[0039] Figure 6a ), Figure 6b )and Figure 6c The image shows the TGA curves of the photoluminescent enhancement materials prepared in Examples 1, 2, and 3.

[0040] Figure 7a (This is a photograph of the fluorescence intensity of the solid-state photoluminescence enhancement material prepared in Example 1 under initial ultraviolet light irradiation.) Figure 7b The image shows the fluorescence intensity of the solid-state photoluminescent enhancement material prepared in Example 1 after 30 seconds of ultraviolet light irradiation. Detailed Implementation

[0041] The principles and features of the present invention are described below with reference to the accompanying drawings. The examples given are only for explaining the present invention and are not intended to limit the scope of the present invention.

[0042] Example 1

[0043] Preparation of solid-state photoluminescence enhancement material as shown in Equation 1.

[0044]

[0045] Weigh 0.65 g of 9-(4-bromophenyl)carbazole, 0.07 g of bis(triphenylphosphine)palladium dichloride, and 0.038 g of CuI, and mix thoroughly in a double-necked flask. Purge the mixture three times with nitrogen under a sealed environment. Under a nitrogen atmosphere, add 15 mL of ultra-dry tetrahydrofuran, 0.56 mL of trimethylethynylsilane, and 10 mL of diisopropylamine using a constant-pressure dropping funnel. React under nitrogen protection at 80 °C for 36 h to carry out the first coumarin coupling reaction. Extract the resulting mixture with dichloromethane and water, and collect the lower organic phase solution. Purify the solution using dry column chromatography with pure petroleum ether as the developing solvent. The resulting white solid powder is the product 9-((4-trimethylsilylethynyl)phenyl)carbazole. The molar ratio of 9-(4-bromophenyl)carbazole to trimethylethynylsilane, bis(triphenylphosphine)palladium dichloride, and CuI is 1:1:0.1:0.1.

[0046] Weigh 1.02 g of 9-((4-trimethylsilylethynyl)phenyl)carbazole and dissolve it in 50 mL of dichloromethane. Then add 4.5 mL of tetrabutylammonium fluoride (TBAF, 1 mol / L THF solution) and stir at room temperature for 30 min. Concentrate the product and extract it with water and ethyl acetate. Since ethyl acetate is slightly soluble in water, excess ethyl acetate can be added, and the product can be extracted with water in small amounts multiple times. The resulting upper organic phase is an ethyl acetate solution containing the product. Iodine indicator can be used to determine whether TBAF has been completely removed. Rotary evaporate the upper organic phase and cool it. The brown solid obtained is the target product 9-p-ethynylphenylcarbazole, with a yield of 78%. The molar ratio of 9-((4-trimethylsilylethynyl)phenyl)carbazole to tetrabutylammonium fluoride is 1:4.

[0047] Weigh 1.215 g of 9-p-ethynylphenylcarbazole, 0.771 g of 9-bromoanthracene, 0.21 g of bis(triphenylphosphine)palladium dichloride, and 0.114 g of CuI, and mix them evenly in a double-necked flask. After purging with nitrogen three times in a sealed environment, add 45 mL of ultra-dry tetrahydrofuran and 45 mL of diisopropylamine using a constant pressure dropping funnel under nitrogen protection at -78 °C and mix evenly. The second sorghum coupling reaction is carried out at 110 °C for 20 h under nitrogen protection. The obtained mixed product was extracted with dichloromethane and water. The lower organic phase solution was collected and purified by dry column chromatography using a petroleum ether:dichloromethane solution with a volume ratio of 5:1 as the developing solvent. The resulting white solid powder was the target product 1-(4-(9-carbazolyl)phenyl)-2-(9-anthrayl)acetylene, wherein the molar ratio of 9-acetylenephenylcarbazole to 9-bromoanthracene, bis(triphenylphosphine)palladium dichloride, and CuI was 1:1:0.1:0.1. The product mass was 0.23 g, with a yield of approximately 10%. 1H NMR(500MHz,Methylene Chloride-d2)δ8.76(d,J=8.7Hz,2H),8.57(s,1H),8.22(d,J=7.8Hz,2H),8.13(d,J=8.4Hz,2H),8 .11–8.06(m,2H),7.77–7.69(m,4H),7.64–7.56(m,4H),7.53–7.48(m,2H),7.37(t,J=7.4Hz,2H).

[0048] Example 2

[0049] Preparation of solid-state photoluminescence enhancement material as shown in Equation 2.

[0050]

[0051] Weigh 0.4 g of tris(dibenzylacetone)palladium, 0.12 g of tri-tert-butylphosphine tetrafluoroborate, and 30 mL of toluene into a single-necked flask. After stirring at room temperature for 10 min, add 6.28 g of sodium tert-butoxide, 2.74 g of carbazole, 2.4 mL of 4-bromostyrene, and 60 mL of toluene solution. Under nitrogen protection, perform a first reflux reaction at 90 °C for 4 h. Extract the resulting mixture with dichloromethane and water, and collect the lower organic phase solution. Purify the product by dry column chromatography using pure petroleum ether as the developing solvent. The resulting white solid powder is the product 1-(4-(9-carbazolyl)phenyl)ethylene. The molar ratio of carbazole, 4-bromostyrene, sodium tert-butoxide, tris(dibenzylacetone)palladium, and tri-tert-butylphosphine tetrafluoroborate is 1.2:1:0.05:0.05.

[0052] Weigh 1 g of 1-(4-(9-carbazolyl)phenyl)ethylene, 1 g of 9-bromoanthracene, 0.6 g of sodium carbonate, 0.07 g of palladium acetate, and 70 mL of N,N-dimethylformamide, and add them to a single-necked flask. Under nitrogen protection, the mixture is subjected to a second reflux reaction at 110 °C for 4 h. The resulting mixture is extracted with dichloromethane and water. The lower organic phase solution is collected and purified by dry column chromatography using petroleum ether:dichloromethane (v / v) = 5:1 as the developing solvent. The resulting white solid powder is the product 1-(4-(9-carbazolyl)phenyl)-2-(9-anthrayl)ethylene. The molar ratio of 1-(4-(9-carbazolyl)phenyl)ethylene, 9-bromoanthracene, sodium carbonate, and palladium acetate is 3.7:3.9:5.6:0.2. The product mass is 1.05 g, with a yield of approximately 58%.

[0053] Example 3

[0054] Preparation of solid-state photoluminescence enhancement material as shown in Equation 3.

[0055]

[0056] Weigh 0.4 g of tris(dibenzylacetone)palladium, 0.12 g of tri-tert-butylphosphine tetrafluoroborate, and 30 mL of toluene into a single-necked flask. After stirring at room temperature for 10 min, add 6.28 g of sodium tert-butoxide, 2.77 g of diphenylamine, 2.4 mL of 4-bromostyrene, and 60 mL of toluene solution. Under nitrogen protection, perform a third reflux reaction at 30 °C for 1 h. Extract the resulting mixture with dichloromethane and water, collect the lower organic phase solution, and purify it by dry column chromatography using pure petroleum ether as the developing solvent. The resulting white solid powder is the product 1-(4-(diphenylamino)phenyl)ethylene. The molar ratio of diphenylamine, 4-bromostyrene, sodium tert-butoxide, tris(dibenzylacetone)palladium, and tri-tert-butylphosphine tetrafluoroborate is 1.2:1:0.05:0.05.

[0057] Weigh 1.2 g of 1-(4-(diphenylamino)phenyl)ethylene, 1 g of 9-bromoanthracene, 0.6 g of sodium carbonate, 0.07 g of palladium acetate, and 70 mL of N,N-dimethylformamide, and add them to a single-necked flask. Under nitrogen protection, the mixture is subjected to a fourth reflux reaction at 110 °C for 4 h. The resulting mixture is extracted with dichloromethane and water. The lower organic phase solution is collected and purified by dry column chromatography using petroleum ether:dichloromethane at a volume ratio of 5:1 as the developing solvent. The resulting white solid powder is the product 1-(4-(diphenylamino)phenyl)-2-(9-anthrayl)ethylene. The molar ratio of 1-(4-(diphenylamino)phenyl)ethylene, 9-bromoanthracene, sodium carbonate, and palladium acetate is 3.7:3.9:5.6:0.2. The product mass is 1.22 g, with a yield of approximately 63%.

[0058] Example 4

[0059] The solid-state photoluminescence-enhancing material powder prepared in Example 1 was placed in a glass petri dish, which was then placed under a microscope. A photograph of the material's fluorescence intensity was taken under UV light irradiation for 0 seconds in a dark environment. Figure 1a As shown in the image, the fluorescence intensity of the material powder is low when not irradiated by a UV lamp. Then, a 365nm UV lamp was placed above the petri dish, and the powder was continuously irradiated for 30 seconds. The fluorescence intensity was then photographed again, as shown in the image. Figure 1b As shown in the figure, the powder in the dark environment changes from an initial low luminescence efficiency state to a high luminescence efficiency fluorescent state, indicating that the fluorescence intensity of the material powder increases visible to the naked eye after irradiation with a UV lamp. Then, the material is placed at 90℃ and 1*10 -2 Heating under a low vacuum of Pa for 5 minutes restored the visible fluorescence intensity of the powder to its state before UV irradiation. Following the same procedure, fluorescence intensity photographs of the solid powders from Examples 2 and 3 were taken before and after photostimulation, as shown below. Figure 2a ), Figure 2b )and Figure 3a ), Figure 3b As shown in the figure. Figure 2a ), Figure 3a This indicates that the fluorescence intensity of the material powder, when not irradiated by a UV lamp, is low and can be seen with the naked eye. Figure 2b ), Figure 3b This indicates that the fluorescence intensity of the material powder increased visibly after irradiation with a UV lamp. All three materials passed the tests at 90℃ and 1*10⁻⁶. - 2 Heating under low vacuum conditions for 5 minutes at Pa can reversibly restore the product to its state before UV irradiation.

[0060] Example 5

[0061] 1-(4-(9-carbazolyl)phenyl)-2-(9-anthrayl)acetylene crystals of Formula 1 were obtained using vapor deposition (heating the compound under low vacuum conditions, with molecules sublimating in the high-temperature region and condensing in the low-temperature region; the sublimation temperature varies depending on the compound to obtain a higher purity). The vacuum level was 1*10. -2 Pa, the high temperature range is 210℃, and the low temperature range is 110℃.

[0062] The photoluminescent quantum yield (PLQY) of 1-(4-(9-carbazolyl)phenyl)-2-(9-anthrayl)acetylene crystals before and after irradiation with a 365 nm UV lamp was measured using an FLS980-S2S2-stm steady-state / transient fluorescence spectrometer.

[0063] Table 1: Relevant data from the test in Example 5

[0064] PLQY 2.99％ 53.33％ Emission peak position (nm) 490 490

[0065] As shown in Table 1, the fluorescence quantum yield of the crystal tested in Example 5 increased from a low 2.99% to 53.33% after irradiation with 365 nm ultraviolet light, and the emission peak position remained unchanged, both exhibiting green light emission. Since the dimer formed by the [4+4] photodimerization of anthracene disrupts the original π-conjugation of the monomer, it often severely damages the luminescence of the product. However, the fluorescence quantum yield of 1-(4-(9-carbazolyl)phenyl)-2-(9-anthrayl)acetylene crystal after the [4+4] photodimerization reaction of anthracene reached nearly 20 times that before the reaction, providing a new material option for enhancing the fluorescence of anthracene [4+4] photodimerization.

[0066] Example 6

[0067] Thermal properties have a very important impact on materials. Thermogravimetric analysis (TGA) of these compounds was performed using a Q 500 thermogravimetric analyzer. The thermal decomposition temperature of compound 1 exceeds 386.5℃ (e.g., Figure 6a As shown in the figure), the thermal decomposition temperature of compound 2 exceeds 375.4℃ (e.g. Figure 6b As shown in the figure), the thermal decomposition temperature of compound 3 exceeds 302.2℃ (e.g. Figure 6c As shown in the figure, it has good thermal stability.

[0068] Example 7

[0069] To illustrate the application of the solid-state photoluminescence enhancement material prepared in Example 1, the material was laid flat in a perforated mold with an "L"-shaped pattern. To highlight the contrast in fluorescence intensity, a non-light-absorbing black cardstock was used as the background, and the environment was a dark room. Initially, the brightness of the "L"-shaped pattern was low under UV light irradiation, such as... Figure 7a As shown in the image; after continuous irradiation with a UV lamp for 30 seconds, the brightness of the "L"-shaped pattern gradually increases during the irradiation process, as... Figure 7b As shown in the image. The material is then removed from the mold and heated to 90°C at 1*10°C. -2 Heated under low vacuum conditions for 5 minutes, the material was placed back into a hollowed-out mold with an "L"-shaped pattern in a dark room and irradiated with ultraviolet light again. The "L"-shaped pattern returned to its initial brightness after ultraviolet light irradiation. This demonstrates that the material exhibits good photoluminescence enhancement and reversibility, making it a promising candidate for applications in stimulus-response applications.

[0070] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A solid-state photoluminescence enhancement material, the structural formula of which is shown below: 。 2. The preparation method of the solid-state photoluminescence enhancement material according to claim 1, comprising the following steps: (1) 9-(4-bromophenyl)carbazole was mixed with trimethylethynylsilane, catalyst and CuI in a solvent to carry out the first coupling reaction. The product was extracted with water and dichloromethane, and purified by column chromatography of the lower organic phase solution. Pure petroleum ether was used as the developing solvent to obtain 9-((4-trimethylsilylethynyl)phenyl)carbazole. (2) Dissolve 9-((4-trimethylsilylethynyl)phenyl)carbazole in dichloromethane, add tetrabutylammonium fluoride to remove the trimethylsilyl group after deprotection, concentrate the product and extract it with water and ethyl acetate, take the upper organic phase for rotary evaporation and cooling to obtain 9-p-ethynylphenylcarbazole. (3) 9-p-acetylenylphenylcarbazole, 9-bromoanthracene, catalyst, and CuI were mixed in a solvent to carry out a second coupling reaction. The product was extracted with water and dichloromethane, and purified by column chromatography of the lower organic phase solution. Petroleum ether:dichloromethane volume ratio = 3~5:1 was used as the developing solvent to obtain 1-(4-(9-carbazolyl)phenyl)-2-(9-anthrayl)acetylene white solid powder as shown in Formula 1.

3. The method for preparing a solid-state photoluminescence enhancement material as described in claim 2, characterized in that: In step (1), the molar ratio of 9-(4-bromophenyl)carbazole to trimethylethynylsilane, catalyst, and CuI is 1:1~1.2:0.1:0.1, and the solvent is a mixture of ultra-dry tetrahydrofuran and diisopropylamine with a volume ratio of 1~3:1; in step (2), the molar ratio of 9-((4-trimethylsilylethynyl)phenyl)carbazole to tetrabutylammonium fluoride is 1:3~5; in step (3), the molar ratio of 9-p-ethynylphenylcarbazole to 9-bromoanthracene, catalyst, and CuI is 1:1~1.2:0.1:0.1, and the solvent is a mixture of ultra-dry tetrahydrofuran and diisopropylamine with a volume ratio of 1~3:

1.

4. The method for preparing a solid-state photoluminescence enhancement material as described in claim 2, characterized in that: In step (1), the reaction temperature of the first coix seed coupling reaction is 70~90°C and the reaction time is 30~40 hours; in step (3), the reaction temperature of the second coix seed coupling reaction is 100~120°C and the reaction time is 15~25 hours; in steps (1) and (3), the catalysts for the first coix seed coupling reaction and the second coix seed coupling reaction are one or two of bis(triphenylphosphine)palladium dichloride and 1,1-bis(diphenylphosphine)ferrocene palladium dichloride dichloromethane complex.

5. The application of the solid-state photoluminescence enhancement material according to claim 1 in the field of photoluminescence enhancement.

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