An aggregation-induced emission material with high fluorescence quantum yield and large stokes shift, and a preparation method and application thereof

Abstract

The application discloses an aggregation-induced emission material with high fluorescence quantum yield and large stokes shift, a preparation method and application thereof, and belongs to the technical field of preparation of the aggregation-induced emission material. The preparation method comprises the following steps: obtaining an intermediate by means of Suzuki-Miyaura coupling reaction of an organic boric acid and bromosalicylaldehyde; and adding the intermediate, sodium metabisulfite and aminophenylthiophenol into an organic solvent, and then performing high-temperature reaction to prepare the aggregation-induced emission material. The aggregation-induced emission material is synthesized by means of a two-step method, can be rapidly and mass-produced, and has the advantages of high fluorescence efficiency, large stokes shift, good stability and the like.

Description

Technical Field

[0001] This invention belongs to the field of aggregation-induced emission material preparation technology, and particularly relates to an aggregation-induced emission material with high fluorescence quantum yield and large Stokes shift, its preparation method and application. Background Technology

[0002] Fluorescent solar concentrators can collect sunlight over a wide area, converting it into high-quantum-efficiency fluorescence, and then using total internal reflection to transmit the fluorescence to optical components at the device's edge. Fluorescent solar concentrators achieve sunlight concentration through three steps: light absorption, fluorescence reflection, and light transmission. Solar cells installed at the edge of the fluorescent concentrator effectively absorb high-intensity fluorescence, thereby improving the photoelectric conversion efficiency per unit area of ​​the solar cell. Common fluorescent groups include: small organic molecules, quantum dot materials, metal complexes, and perovskite materials. Among these, the phenomenon of spectral overlap between absorption and emission in fluorescent materials is called self-absorption (reabsorption). Self-absorption significantly reduces the fluorescence intensity reaching the device edge during fluorescence transmission, thus weakening the photoelectric conversion efficiency of the fluorescent solar concentrator. The impact of self-absorption on fluorescent solar concentrators is affected by the material's size; generally, larger material areas result in lower efficiency. Furthermore, fluorescence quantum efficiency is also a major factor limiting the efficiency of fluorescent solar concentrators. Typically, materials with large Stokes shifts (low self-absorption effect) have lower fluorescence quantum efficiencies.

[0003] Therefore, there is an urgent need to provide an aggregation-induced emission material with both high fluorescence quantum yield and large Stokes shift, and a method for its preparation. Summary of the Invention

[0004] To overcome the shortcomings of strong self-absorption and low efficiency in existing fluorescent solar concentrators, this invention proposes an aggregation-induced emission material with high fluorescence quantum yield and large Stokes shift, along with its preparation method and applications. An organic small molecule material with excited-state intramolecular proton transfer (ESIPT) effect is designed, specifically by modifying its spectrum and functional groups at different chemical sites to alter the absorption and emission spectra, fluorescence quantum efficiency, Stokes shift, and aggregation effect. This material is then synthesized via a two-step method. This approach not only offers the advantages of rapid and large-scale preparation but also enables the prepared aggregation-induced emission material to possess high fluorescence efficiency, a large Stokes shift, and good stability.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] One of the technical solutions of this invention:

[0007] An aggregation-induced emission material with large Stokes shift and high fluorescence quantum efficiency comprises the following structure:

[0008] .

[0009] Beneficial effects: Through molecular structure design and aggregation state structure adjustment, this invention enables aggregation-induced emission materials to have large Stokes shift and high fluorescence quantum efficiency, completely eliminating self-absorption, thereby preparing a fluorescent solar concentrator with both high efficiency and low loss.

[0010] The second technical solution of the present invention:

[0011] A method for preparing an aggregation-induced emission material with large Stokes shift and high fluorescence quantum efficiency includes the following steps:

[0012] The intermediate was obtained by coupling organoboronic acid and bromosalicylaldehyde via the Suzuki-Miyaura reaction.

[0013] The intermediate, sodium metabisulfite, and aminobenzylthiophenol were added to an organic solvent and then reacted at high temperature to prepare the aggregation-induced emission material.

[0014] Preferably, the organoboronic acid includes any one of mesimilar trimethylphenylboronic acid, mesimilar triisopropylphenylboronic acid, 9-anthracite or acridine-9-ylboronic acid.

[0015] Preferably, the brominated salicylaldehyde is 3-bromosalicylic acid aldehyde, 4-bromosalicylic acid aldehyde, or 5-bromosalicylic acid aldehyde.

[0016] Preferably, the molar ratio of the organoboronic acid to bromosalicylaldehyde is (1.4-2):1; more preferably, the molar ratio of the organoboronic acid to bromosalicylaldehyde is 7:5.

[0017] The molar ratio of the intermediate, sodium metabisulfite, and aminothiophenol is 1:1:(1.2-2); more preferably, the molar ratio of the intermediate, sodium metabisulfite, and aminothiophenol is 5:5:6.

[0018] Preferably, the specific process of the Suzuki-Miyaura coupling reaction is as follows:

[0019] The intermediate was prepared by mixing the brominated salicylaldehyde, organoboronic acid, and phosphorus ligand under an inert atmosphere, with a catalyst and an alkaline salt, and then heating.

[0020] Furthermore, the inert atmosphere is nitrogen; and / or

[0021] The catalyst is palladium acetate; and / or

[0022] The alkaline salt comprises any one of anhydrous potassium phosphate, sodium tert-butoxide, or potassium carbonate; and / or

[0023] The phosphorus ligand is any one of R-Phos (2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl), S-Phos (2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl), or X-Phos (2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl) ligands.

[0024] Furthermore, the heating process is as follows: reacting at 105℃-110℃ for 12-48 hours; more preferably, reacting at 105℃ for 12 hours.

[0025] Furthermore, the heating process is followed by cooling and purification processes.

[0026] Furthermore, the purification process involves: extracting the crude product obtained by cooling with a system of water and dichloromethane, and then removing the solvent by vacuum distillation; the crude product obtained is then separated by column chromatography using ethyl acetate and petroleum ether.

[0027] Preferably, the organic solvent is N,N-dimethylformamide.

[0028] Preferably, the conditions for the high-temperature reaction process are: reacting at 140°C for 2-4 hours.

[0029] The third technical solution of this invention:

[0030] Application of aggregation-induced emission materials with large Stokes shift and high fluorescence quantum efficiency in the preparation of fluorescent solar concentrators.

[0031] Fourth technical solution of the present invention:

[0032] A fluorescent solar concentrator is prepared from the above-mentioned aggregation-induced emission material.

[0033] Preferably, the fluorescent solar concentrator, in addition to the base layer, also includes an optical waveguide layer containing the aggregation-induced light-emitting material.

[0034] Fifth technical solution of the present invention:

[0035] The method for preparing the fluorescent solar concentrator includes the following steps:

[0036] The aggregation-induced light-emitting material and the mixed solvent were subjected to ultrasonic treatment in sequence to obtain a mixed solution;

[0037] The mixed solution is scraped onto the surface of the substrate and then heated to obtain the fluorescent solar concentrator.

[0038] Preferably, the mixed solvent is composed of polymethyl methacrylate and toluene; wherein the concentration of polymethyl methacrylate is 18-22%.

[0039] Preferably, the duration of the ultrasound process is 20 minutes.

[0040] Preferably, the concentration of the aggregation-induced emission material in the mixed solution is 2.1%-6.3%.

[0041] Preferably, the conditions during the heat treatment process are: solvent evaporation to form a film in an oven at 80°C for 48 hours.

[0042] Compared with the prior art, the present invention has the following advantages and technical effects:

[0043] This invention designs and synthesizes aggregation-induced emission materials with excited-state intramolecular proton transfer (ESIPT) effect. By adjusting the aggregation state structure, the quantum yield and Stokes shift of small organic molecules in the aggregation state are significantly improved, approaching 200 nm.

[0044] This invention utilizes a coating technique to bond aggregation-induced emission materials with high quantum yield and large Stokes shift onto a glass surface to form an optical waveguide layer, thereby fabricating a fluorescent solar concentrator. By testing the photoelectric conversion efficiency of fluorescent solar concentrators of different sizes, it was demonstrated that the efficiency decreases only slightly with increasing size, maintaining an efficiency of 0.41% even at a size of 400 square centimeters (photoelectric conversion efficiency = solar cell power / solar power). Attached Figure Description

[0045] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings:

[0046] Figure 1 This is a photograph taken under sunlight of the fluorescent solar concentrator prepared in Example 5.

[0047] Figure 2 The fluorescence quantum yield diagrams of compounds C1, C2, and C3 prepared in Example 2 are shown.

[0048] Figure 3 The graph shows the current density-voltage characteristic curves (JV characteristic curves) of fluorescent solar concentrators of different sizes prepared in Example 5 under sunlight.

[0049] Figure 4 This is a chemical synthesis route diagram for preparing A1, A2, and A3 in Example 1 of the present invention;

[0050] Figure 5 The absorption and emission spectra of compound C1 prepared in Example 2 of this invention are shown. Detailed Implementation

[0051] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0052] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0053] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0054] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be readily apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0055] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0056] Unless otherwise specified, "room temperature" in this invention refers to 20-30℃.

[0057] All raw materials used in this invention were purchased from the market.

[0058] The technical solution of the present invention will be further illustrated by the following embodiments.

[0059] Example 1

[0060] like Figure 4As shown, a method for preparing an aggregation-induced emission material with large Stokes shift and high fluorescence quantum efficiency includes the following steps:

[0061] 1. Preparation of A1a, A2a, and A3a:

[0062] In a nitrogen atmosphere, 10 mmol of 3-bromosalicylic acid was added to a 250 mL three-necked flask, followed by 14 mmol of mesityleneboronic acid and 60 mmol of anhydrous potassium phosphate. 90 mL of toluene and 15 mL of water were then added to the system for deoxygenation. Finally, 0.50 mmol of palladium acetate catalyst and 1 mmol of R-Phos ligand were added. The reaction mixture was incubated at 105 °C for 12 h, and the reaction progress was monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature. The crude product was extracted with a system of water and dichloromethane, and the solvent was removed by vacuum distillation. The crude product was separated by column chromatography using ethyl acetate and petroleum ether (volume ratio 2:98) to obtain a colorless oily product, A1a.

[0063] Among them, A1a (yield 98%). 1 H NMR (500 MHz, CDCl3) δ 11.21 (s, 1H), 9.98 (s,1H), 7.48 (s, 1H), 7.48 – 7.39 (m, 1H), 7.19 (d, J = 8.4 Hz, 1H), 7.12 (s,2H), 2.48 (s, 3H), 2.20 (s, 6H);

[0064] The preparation process of A2a is the same as that of A1a, except that 3-bromosalicylic acid is replaced with 4-bromosalicylic acid. A2a (yield 95%). 1 H NMR (500 MHz, CDCl3) δ 11.32 – 11.26 (m, 1H), 10.03 – 9.97 (m,1H), 7.70 (td, J = 7.8, 4.7 Hz, 1H), 7.07 – 7.03 (m, 2H), 6.97 – 6.90 (m,2H), 2.52 – 2.38 (m, 3H), 2.18 – 2.12 (m, 6H);

[0065] The preparation process of A3a is the same as that of A1a, except that 3-bromosalicylic acid is replaced with 5-bromosalicylic acid. A3a (yield 97%). 1H NMR (500 MHz, CDCl3) δ 11.28 (t, J = 2.9 Hz, 1H), 10.04 – 9.97(m, 1H), 7.54 – 7.50 (m, 1H), 7.50 – 7.44 (m, 1H), 7.23 (dd, J = 7.4, 4.5 Hz,1H), 7.16 (s, 2H), 2.53 (d, J = 4.0 Hz, 3H), 2.25 (t, J = 3.3 Hz, 6H).

[0066] 2. Preparation process of compounds A1, A2, and A3:

[0067] A colorless oily product A1a (5 mmol), sodium metabisulfite (5 mmol), and aminobenzylthiophenol (6 mmol) were added to 20 mL of N,N-dimethylformamide. The reaction mixture was reacted at 140 °C for 4 h, and the reaction progress was monitored using TLC. After the reaction was complete, the reaction solution was cooled to room temperature, and a large amount of water was added, producing a large amount of crude product. The crude product was washed with a large amount of methanol to obtain a white powder product A1, with a yield of 92%.

[0068] The preparation process of A2 is the same as that of A1, except that A1a is replaced with A2a. The yield of A2 is 90%.

[0069] The preparation process of A3 is the same as that of A1, except that A1a is replaced with A3a. The yield of A3 is 95%.

[0070] Example 2

[0071] A method for preparing an aggregation-induced emission material with large Stokes shift and high fluorescence quantum efficiency includes the following steps:

[0072] 1. Preparation of C1a, C2a, C3a

[0073] In a nitrogen atmosphere, 3-bromosalicylic acid (10 mmol), 9-anthraboronic acid (14 mmol), and anhydrous potassium phosphate (60 mmol) were added to a 250 mL three-necked flask. 90 mL of toluene and 15 mL of water were then added to the system for deoxygenation. Finally, palladium acetate catalyst (0.50 mmol) and R-Phos ligand (1 mmol) were added. The reaction mixture was reacted at 105 °C for 12 h, and the reaction progress was monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature. The crude product was extracted with water and dichloromethane, and the solvent was removed by vacuum distillation. The crude product was separated by column chromatography using ethyl acetate and petroleum ether (volume ratio 2:98) to obtain a white crystalline product C1a (yield 94%). 1 H NMR (500 MHz, CDCl3) δ 11.18 (s, 1H), 10.08 (s, 1H), 8.55 (s, 1H), 8.07 (d, J = 8.5 Hz, 2H), 7.80 (dd, J = 7.8, 1.8 Hz, 1H), 7.60 – 7.57 (m, 3H), 7.47 (ddd, J = 8.1,6.5, 1.1 Hz, 2H), 7.38 (ddd, J = 8.1, 6.5, 1.3 Hz, 2H), 7.28 (d, J = 7.5 Hz,1H);

[0074] The preparation process of C2a is the same as that of C1a, except that 3-bromosalicylic acid is replaced with 4-bromosalicylic acid. The resulting pale yellow crystalline powder C2a (yield 98%) was obtained. 1 H NMR (500 MHz, CDCl3) δ 11.23 (s, 1H),10.07 (s, 1H), 8.54 (s, 1H), 8.06 (d, J = 8.5 Hz, 2H), 7.77 (d, J = 7.6 Hz,1H), 7.63 (dd, J = 8.9, 1.2 Hz, 2H), 7.48 (ddd, J = 8.4, 6.6, 1.1 Hz, 2H), 7.39 (ddd, J = 8.9, 6.4, 1.3 Hz, 2H), 7.14 – 7.09 (m, 2H);

[0075] The preparation process of C3a is the same as that of C1a, except that 3-bromosalicylic acid is replaced with 5-bromosalicylic acid. The resulting white crystalline product is C3a (yield 95%). 1H NMR (500 MHz, CDCl3) δ 11.19 (s, 1H), 9.95 (s, 1H), 8.54 (s, 1H), 8.07 (d, J = 8.5 Hz, 2H), 7.65 (dd, J = 9.1, 1.5 Hz,3H), 7.61 (dd, J = 8.4, 2.2 Hz, 1H), 7.49 (ddd, J = 8.3, 6.6, 1.1 Hz, 2H), 7.39 (ddd, J = 8.8, 6.5, 1.3 Hz, 2H), 7.24 (d, J = 8.4 Hz, 1H).

[0076] 2. Preparation process of compounds C1, C2, and C3:

[0077] C1a (5 mmol), sodium metabisulfite (5 mmol), and aminobenzylthiophenol (6 mmol) were added to 20 mL of N,N-dimethylformamide. The reaction mixture was reacted at 140 °C for 4 h, and the reaction progress was monitored using TLC. After the reaction was complete, the reaction solution was cooled to room temperature, and a large amount of water was added, producing a large amount of crude product. The crude product was washed with a large amount of methanol to obtain a white powder product C1 (yield 97%). 1 H NMR (500 MHz, CDCl3) δ 8.56 (s, 1H), 8.09 (d, J =8.5 Hz, 2H), 7.98 – 7.91 (m, 2H), 7.81 (d, J = 8.0 Hz, 1H), 7.74 (d, J = 8.8Hz, 2H), 7.51 – 7.35 (m, 7H), 7.21 (t, J = 7.6 Hz, 1H);

[0078] The preparation process of C2 is the same as that of C1, except that C1a is replaced with C2a. The obtained C2 (yield 94%)... 1H NMR (500 MHz, CDCl3) δ 8.56 (s, 1H), 8.10 (d, J = 8.3 Hz, 3H), 8.01 (d, J = 7.9 Hz, 1H), 7.94 (d, J = 7.9 Hz, 1H), 7.82 (d, J = 8.8 Hz, 2H), 7.63 – 7.56 (m, 1H), 7.55 – 7.47 (m, 3H), 7.43 (ddd, J = 8.9, 6.4, 1.3 Hz, 2H), 7.29 (d, J = 8.8 Hz, 2H), 7.09 (dd, J = 7.9, 1.6 Hz, 1H;

[0079] The preparation process of C3 is the same as that of C1 described above, except that C1a is replaced with C3a. The obtained C3 (yield 92%)... 1 H NMR (500 MHz, CDCl3) δ 8.54 (s, 1H), 8.07 (dd, J = 12.7, 8.4 Hz,3H), 7.85 (d, J = 7.9 Hz, 1H), 7.83 – 7.72 (m, 3H), 7.55 – 7.46 (m, 4H), 7.43– 7.37 (m, 3H), 7.35 (d, J = 8.3 Hz, 1H).

[0080] Example 3

[0081] In a nitrogen atmosphere, 10 mmol of 3-bromosalicylic acid, 14 mmol of triisopropylphenylboronic acid, and 60 mmol of anhydrous potassium phosphate were added to a 250 mL three-necked flask. 90 mL of toluene and 15 mL of water were added to the system for deoxygenation treatment. Finally, 0.50 mmol of palladium acetate catalyst and 1 mmol of R-Phos ligand were added. The reaction mixture was reacted at 110 °C for 12 h, and the reaction progress was monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature, and the crude product was extracted with water and dichloromethane, followed by solvent removal by vacuum distillation. The crude product was separated by column chromatography using ethyl acetate and petroleum ether (volume ratio 2:98) to obtain a white intermediate (yield 84%). The white intermediate (5 mmol), sodium metabisulfite (5 mmol), and aminothiophenol (6 mmol) were added to 20 mL of N,N-dimethylformamide. The reaction mixture was reacted at 140°C for 4 hours, and the reaction progress was monitored using a TLC plate. After the reaction was completed, the reaction solution was cooled to room temperature, and a large amount of water was added, which produced a large amount of crude product. The crude product was washed with a large amount of methanol to obtain a white powder product B1 (yield 97%).

[0082] The preparation process of B2 is the same as that of B1, except that 3-bromosalicylic acid aldehyde is replaced with 4-bromosalicylic acid aldehyde. The resulting B2 (yield 92%).

[0083] The preparation process of B3 is the same as that of B1, except that 3-bromosalicylic acid is replaced with 5-bromosalicylic acid. The resulting B3 has a yield of 93%.

[0084] Example 4

[0085] In a nitrogen atmosphere, 10 mmol of 3-bromosalicylic acid, 14 mmol of acridine-9-ylboronic acid, and 60 mmol of anhydrous potassium phosphate were added to a 250 mL three-necked flask. 90 mL of toluene and 15 mL of water were added to the system for deoxygenation treatment. Finally, 0.50 mmol of palladium acetate catalyst and 1 mmol of R-Phos ligand were added. The reaction mixture was reacted at 110 °C for 12 h, and the reaction progress was monitored by TLC. After the reaction was complete, the reaction solution was cooled to room temperature. The crude product was extracted with water and dichloromethane, and the solvent was removed by vacuum distillation. The crude product was separated by column chromatography using ethyl acetate and petroleum ether (volume ratio 5:95) to obtain a white intermediate (75% yield). The pale yellow intermediate (5 mmol), sodium metabisulfite (5 mmol), and aminothiophenol (6 mmol) were added to 20 mL of N,N-dimethylformamide. The reaction mixture was reacted at 140℃ for 4 hours, and the reaction progress was monitored by TLC. After the reaction was completed, the reaction solution was cooled to room temperature and a large amount of water was added, which produced a large amount of crude product. The crude product was washed with a large amount of methanol to obtain a pale yellow powder product D1 (yield 90%).

[0086] The preparation process of D2 is the same as that of D1, except that 3-bromosalicylaldehyde is replaced with 4-bromosalicylaldehyde. The resulting D2 (yield 92%) was obtained.

[0087] The preparation process of D3 is the same as that of D1, except that 3-bromosalicylic acid is replaced with 5-bromosalicylic acid. The resulting D3 (yield 88%).

[0088] Example 5: Preparation process of a fluorescent solar concentrator:

[0089] 5g of polymethyl methacrylate (PMMA) was dissolved in a certain amount of toluene and stirred until completely dissolved to prepare a solution with a specific gravity of 18-22% (PMMA by mass). A certain amount of the C1 compound prepared in Example 2 was taken, and the two were mixed evenly and sonicated for 20 minutes to completely remove air bubbles, preparing a solution with a specific gravity of 6.3% (C1 compound by mass). The resulting solution was coated onto the surface of a glass substrate using a coating machine and placed in an 80°C oven for solvent evaporation to form a film. The evaporation time was 48 hours, resulting in a high fluorescence quantum yield and low loss aggregation-induced emission material for the preparation of a fluorescent solar concentrator (film thickness of 20 μm).

[0090] Example 6: Preparation process of a fluorescent solar concentrator:

[0091] The difference from Example 5 is that a solution with a C1 compound concentration of 4.2% by gravity was prepared. All other steps and conditions were the same as in Example 5.

[0092] Example 7: Preparation process of a fluorescent solar concentrator:

[0093] The difference from Example 5 is that a solution with a C1 compound concentration of 2.1% by gravity was prepared. All other steps and conditions were the same as in Example 5.

[0094] Example 8: Preparation process of a fluorescent solar concentrator:

[0095] The difference from Example 5 is that the C1 compound is replaced with the C3 compound. All other steps and conditions are the same as in Example 5.

[0096] Example 9: Preparation process of a fluorescent solar concentrator:

[0097] The difference from Example 6 is that the C1 compound is replaced with the C3 compound. All other steps and conditions are the same as in Example 6.

[0098] Example 10: Preparation process of a fluorescent solar concentrator:

[0099] The difference from Example 7 is that the C1 compound is replaced with the C3 compound. All other steps and conditions are the same as in Example 7.

[0100] Figure 1 This is a photograph taken under sunlight of the fluorescent solar concentrator prepared in Example 5 of the present invention. Figure 1 It can be seen that it has the advantages of being colorless and highly transparent, and the glass edges produce strong fluorescence.

[0101] Figure 2 The figures show the fluorescence quantum yields of compounds C1, C2, and C3 prepared in Example 2 of this invention. All three compounds exhibit a significant increase in fluorescence quantum yield in the aggregated state (both thin film and crystalline states), demonstrating the presence of aggregation-induced emission (AIE) and its potential to provide high efficiency for fluorescent solar concentrators. The thin film state refers to the compound being doped at a mass percentage of 2.1% in a 100 mg / mL tetrahydrofuran solution of polymethyl methacrylate and then spin-coated into a film. The crystalline state refers to the compound obtained by solvent evaporation in a saturated chloroform solution.

[0102] Figure 3 This is a graph showing the current density-voltage characteristic curve (JV characteristic curve) of the fluorescent solar concentrator prepared in Example 5 of the present invention under sunlight. Figure 3As can be seen, its photoelectric conversion efficiency does not decrease significantly with the increase of size, proving that its efficiency decreases only slightly with the increase of size.

[0103] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. The application of an aggregation-induced emission material with large Stokes shift and high fluorescence quantum efficiency in the preparation of fluorescent solar concentrators, characterized in that, The structural formula of the aggregation-induced emission material is: , and .

2. The application of the aggregation-induced emission material with large Stokes shift and high fluorescence quantum efficiency as described in claim 1 in the field of preparing fluorescent solar concentrators, characterized in that, The preparation method of the aggregation-induced emission material with large Stokes shift and high fluorescence quantum efficiency includes the following steps: The intermediate was obtained by coupling 9-anthraboronic acid and bromosalicylaldehyde via the Suzuki-Miyaura reaction. The intermediate, sodium metabisulfite, and aminobenzylthiophenol were added to an organic solvent and then reacted at high temperature to prepare the aggregation-induced emission material. The bromosalicylaldehyde is 3-bromosalicylaldehyde, 4-bromosalicylaldehyde, or 5-bromosalicylaldehyde.

3. The application of the aggregation-induced emission material with large Stokes shift and high fluorescence quantum efficiency as described in claim 2 in the field of preparing fluorescent solar concentrators, characterized in that, The molar ratio of 9-anthraboronic acid and bromosalicylaldehyde is (1.4-2):1; The molar ratio of the intermediate, sodium metabisulfite, and aminobenzylthiophenol is 1:1:(1.2-2).

4. The application of the aggregation-induced emission material with large Stokes shift and high fluorescence quantum efficiency as described in claim 2 in the field of preparing fluorescent solar concentrators, characterized in that, The specific process of the Suzuki-Miyaura coupling reaction is as follows: The intermediate was prepared by mixing the bromosalicylaldehyde, 9-anthraboronic acid, and phosphorus ligand under an inert atmosphere, with a catalyst and an alkaline salt, and then heating.

5. The application of the aggregation-induced emission material with large Stokes shift and high fluorescence quantum efficiency as described in claim 4 in the field of preparing fluorescent solar concentrators, characterized in that, The heating process is as follows: react at 105℃-110℃ for 12-48 hours.

6. The application of the aggregation-induced emission material with large Stokes shift and high fluorescence quantum efficiency as described in claim 2 in the field of preparing fluorescent solar concentrators, characterized in that, The conditions for the high-temperature reaction process are: reacting at 140℃ for 2-4 hours.

7. A fluorescent solar concentrator, comprising a base layer, characterized in that, It also includes an optical waveguide layer containing the aggregation-induced light-emitting material as described in claim 1.

8. A method for preparing a fluorescent solar concentrator, characterized in that, Includes the following steps: The aggregation-induced light-emitting material described in claim 1 is mixed with a mixed solvent, and then subjected to ultrasonic treatment to obtain a mixed solution; The mixed solution is scraped onto the surface of the substrate and then heated to obtain the fluorescent solar concentrator as described in claim 7.

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