Crown ether derivative as well as solid-state luminescence regulation method and application thereof

Abstract

The invention discloses a crown ether derivative and a solid-state luminescence regulation method and application thereof, and relates to the technical field of luminescent materials. The crown ether derivative is selected from crown ether derivatives A, B or C, and the derivative has a specific conjugated structure. The crown ether derivative provided by the invention shows excellent luminescence property in a solid state, and can effectively avoid interference of flow characteristics and solvent molecules in a solution phase.

Description

Technical Field

[0001] The present invention relates to the technical field of luminescent materials, and particularly to a crown ether derivative, a method for regulating its solid-state luminescence, and applications thereof. Background Art

[0002] Organic solid-state luminescent materials have received extensive attention in the fields of luminescent devices, organic semiconductors, and environmental monitoring due to their advantages such as adjustable structure, low toxicity, and good biocompatibility. Among them, although single-molecule covalent systems containing donor-acceptor structures exhibit excellent performance, their synthesis process is cumbersome, the types of materials are limited, and it is difficult to meet the actual needs. There is an urgent need to develop new solid-state luminescent materials with simple synthesis and rich varieties.

[0003] As the first generation of supramolecular macrocycles, crown ethers have been widely used in the fields of supramolecular polymers, molecular machines, and sensing detection. However, the research on the luminescence properties of crown ethers mostly focuses on the solution phase, which is easily interfered by the flow characteristics and solvent molecules, and has poor stability, limiting their application in complex environments.

[0004] Combining crown ethers with solid-state luminescent materials can effectively avoid the problems in the solution phase, and through molecular structure design, it is expected to obtain new derivatives with adjustable luminescence properties, showing broad application prospects in the field of solid-state luminescent materials. Summary of the Invention

[0005] One of the purposes of the present invention is to provide a novel crown ether derivative, which exhibits excellent luminescence properties in the solid state and can effectively avoid the interference of flow characteristics and solvent molecules in the solution phase.

[0006] To achieve the above purpose, the present invention adopts the following technical solutions:

[0007] A crown ether derivative, selected from crown ether derivative A, B, or C, the derivative has a specific conjugated structure, wherein the structural formula of crown ether derivative A is as shown in formula A, the structural formula of crown ether derivative B is as shown in formula B, and the structural formula of crown ether derivative C is as shown in formula C:

[0008]

[0009] Among them, the crown ether derivative A can be prepared through the following steps:

[0010] S1. Synthesis of intermediate A-1: In an organic solvent, add triethylene glycol, p-toluenesulfonyl chloride, and triethylamine and react to obtain intermediate A-1;

[0011] S2. Synthesis of intermediate A-2: In an organic solvent, under a protective gas environment, add intermediate A-1, hydroquinone, and potassium carbonate and react to obtain intermediate A-2;

[0012] S3. Synthesis of Intermediate A-3: In an organic solvent, Intermediate A-2, p-toluenesulfonyl chloride and triethylamine are added and reacted to obtain Intermediate A-3;

[0013] S4. Synthesis of Crown Ether Derivative A: In an organic solvent, under a protective gas environment, Intermediate A-3, hydroquinone and cesium carbonate are added and reacted to obtain Crown Ether Derivative A.

[0014] Furthermore, in the preparation method of Crown Ether Derivative A:

[0015] In step S1, the molar ratio of triethylene glycol to p-toluenesulfonyl chloride is (1 - 5):1 (e.g., 3:1), the reaction time is 10 - 20 hours (e.g., 16 hours); the reaction temperature is room temperature, and the organic solvent is selected from at least one of 1,2-dichloroethane, chloroform, and dichloromethane (such as one), for example, dichloromethane. Among them, for every 100 mL of organic solvent (such as dichloromethane), 30.0 mmol of triethylene glycol, 10.0 mmol of p-toluenesulfonyl chloride, and 30.0 mmol of triethylamine are corresponding.

[0016] In step S2, the molar ratio of Intermediate A-1 to hydroquinone is (1 - 5):1 (e.g., 42.3:19.2, approximately 2.2:1), the reaction time is 40 - 50 hours (e.g., two days, i.e., 48 hours), and the reaction temperature is 70 - 90 °C; the protective gas is selected from one of nitrogen and argon, for example, nitrogen; the organic solvent is selected from at least one of tetrahydrofuran, acetonitrile, and acetone (such as one), for example, acetonitrile. Among them, for every 280 mL of organic solvent (such as acetonitrile), 42.3 mmol of Intermediate A-1, 19.2 mmol of hydroquinone, and 76.8 mmol of potassium carbonate are corresponding.

[0017] In step S3, the molar ratio of Intermediate A-2 to p-toluenesulfonyl chloride is (0.1 - 0.5):1 (e.g., 19.2:96.1, approximately 0.2:1), the reaction time is 10 - 20 hours (e.g., 16 hours); the reaction temperature is room temperature, and the organic solvent is selected from at least one of 1,2-dichloroethane, chloroform, and dichloromethane (such as one), for example, dichloromethane. Among them, for every 300 mL of organic solvent (such as dichloromethane), 19.2 mmol of Intermediate A-2, 96.1 mmol of p-toluenesulfonyl chloride, and 96.1 mmol of triethylamine are corresponding.

[0018] In step S4, the molar ratio of intermediate A-3 to hydroquinone is (0.5 to 1.5):1 (e.g., 1:1), the reaction time is 48 - 72 hours (e.g., two days, i.e., 48 hours), and the reaction temperature is 100 - 120 °C (e.g., 100 °C); the protective gas is selected from one of nitrogen and argon, e.g., nitrogen; the organic solvent is selected from at least one of acetonitrile, acetone, and N,N-dimethylformamide (such as one), e.g., N,N-dimethylformamide. For every 315 mL of organic solvent (such as N,N-dimethylformamide), there are 12.5 mmol of intermediate A-3, 12.5 mmol of hydroquinone, and 62.5 mmol of cesium carbonate.

[0019] Among them, the crown ether derivative B can be prepared through the following steps:

[0020] S1. Synthesis of intermediate B-1: In an organic solvent, add triethylene glycol, p-toluenesulfonyl chloride, and triethylamine and react to obtain intermediate B-1;

[0021] S2. Synthesis of intermediate B-2: In an organic solvent, add intermediate B-1, 1,4-dihydroxynaphthalene, and potassium carbonate under a protective gas environment and react to obtain intermediate B-2;

[0022] S3. Synthesis of intermediate B-3: In an organic solvent, add intermediate B-2, p-toluenesulfonyl chloride, and triethylamine and react to obtain intermediate B-3;

[0023] S4. Synthesis of crown ether derivative B: In an organic solvent, add intermediate B-3, hydroquinone, and cesium carbonate under a protective gas environment and react to obtain crown ether derivative B.

[0024] Furthermore, in the preparation method of crown ether derivative B:

[0025] In step S1, the molar ratio of triethylene glycol to p-toluenesulfonyl chloride is (1 to 5):1 (e.g., 3:1), the reaction time is 10 - 20 hours (e.g., 16 hours); the reaction temperature is room temperature, and the organic solvent is selected from at least one of 1,2-dichloroethane, chloroform, and dichloromethane (such as one), e.g., dichloromethane. Among them, for every 100 mL of organic solvent (such as dichloromethane), there are 30.0 mmol of triethylene glycol, 10.0 mmol of p-toluenesulfonyl chloride, and 30.0 mmol of triethylamine.

[0026] In step S2, the molar ratio of intermediate B-1 to 1,4-dihydroxynaphthalene is (1 to 5):1 (e.g., 43.5:19.8, approximately 2.2:1), the reaction time is 40 - 50 hours (e.g., two days, i.e., 48 hours), and the reaction temperature is 70 - 90 °C; the protective gas is selected from one of nitrogen and argon, e.g., nitrogen; the organic solvent is selected from at least one of tetrahydrofuran, acetonitrile, and acetone (such as one), e.g., acetonitrile. Among them, for every 280 mL of organic solvent (such as acetonitrile), there are 43.5 mmol of intermediate B-1, 19.8 mmol of 1,4-dihydroxynaphthalene, and 79.2 mmol of potassium carbonate.

[0027] In step S3, the molar ratio of intermediate B-2 to p-toluenesulfonyl chloride is (0.1 to 0.5):1 (e.g., 19.8:99.0, approximately 0.2:1), the reaction time is 10 - 20 hours (e.g., 16 hours); the reaction temperature is room temperature, and the organic solvent is selected from at least one of 1,2-dichloroethane, chloroform, and dichloromethane (such as one), e.g., dichloromethane. Among them, for every 300 mL of organic solvent (such as dichloromethane), there are 19.8 mmol of intermediate B-2, 99.0 mmol of p-toluenesulfonyl chloride, and 99.0 mmol of triethylamine.

[0028] In step S4, the molar ratio of intermediate B-3 to hydroquinone is (0.5 to 1.5):1 (e.g., 1:1), the reaction time is 48 - 72 hours (e.g., 2 days, i.e., 48 hours), and the reaction temperature is 100 - 120 °C (e.g., 100 °C); the protective gas is selected from one of nitrogen and argon, e.g., nitrogen; the organic solvent is selected from at least one of acetonitrile, acetone, and N,N-dimethylformamide (such as one), e.g., N,N-dimethylformamide. Among them, for every 300 mL of organic solvent (such as N,N-dimethylformamide), there are 11.8 mmol of intermediate B-3, 11.8 mmol of hydroquinone, and 59.1 mmol of cesium carbonate.

[0029] Among them, the crown ether derivative C can be prepared through the following steps:

[0030] S1. Synthesis of intermediate C-1: In an organic solvent, add triethylene glycol, p-toluenesulfonyl chloride, and triethylamine for reaction to obtain intermediate C-1;

[0031] S2. Synthesis of intermediate C-2: In an organic solvent, under a protective gas environment, add intermediate C-1, 1,4-dihydroxyanthracene, and potassium carbonate for reaction to obtain intermediate C-2;

[0032] S3. Synthesis of intermediate C-3: In an organic solvent, add intermediate C-2, p-toluenesulfonyl chloride, and triethylamine for reaction to obtain intermediate C-3;

[0033] S4. Synthesis of crown ether derivative C: In an organic solvent, intermediate C-3, hydroquinone, and cesium carbonate are added and reacted under a protective gas atmosphere to obtain crown ether derivative C.

[0034] Furthermore, in the preparation method of crown ether derivative C:

[0035] In step S1, the molar ratio of triethylene glycol to p-toluenesulfonyl chloride is (1 - 5):1 (e.g., 3:1), the reaction time is 10 - 20 hours (e.g., 16 hours); the reaction temperature is room temperature, and the organic solvent is selected from at least one of 1,2-dichloroethane, chloroform, and dichloromethane (such as one), e.g., dichloromethane. Among them, for every 100 mL of organic solvent (such as dichloromethane), there are 30.0 mmol of triethylene glycol, 10.0 mmol of p-toluenesulfonyl chloride, and 30.0 mmol of triethylamine.

[0036] In step S2, the molar ratio of intermediate C-1 to 1,4-dihydroxyanthracene is (1 - 5):1 (e.g., 43.1:19.6, approximately 2.2:1), the reaction time is 40 - 50 hours (e.g., two days, i.e., 48 hours), and the reaction temperature is 70 - 90 °C; the protective gas is selected from one of nitrogen and argon, e.g., nitrogen; the organic solvent is selected from at least one of tetrahydrofuran, acetonitrile, and acetone (such as one), e.g., acetonitrile. Among them, for every 280 mL of organic solvent (such as acetonitrile), there are 43.1 mmol of intermediate C-1, 19.6 mmol of 1,4-dihydroxyanthracene, and 78.4 mmol of potassium carbonate.

[0037] In step S3, the molar ratio of intermediate C-2 to p-toluenesulfonyl chloride is (0.1 - 0.5):1 (e.g., 19.6:98.0, approximately 0.2:1), the reaction time is 10 - 20 hours (e.g., 16 hours); the reaction temperature is room temperature, and the organic solvent is selected from at least one of 1,2-dichloroethane, chloroform, and dichloromethane (such as one), e.g., dichloromethane. Among them, for every 300 mL of organic solvent (such as dichloromethane), there are 19.6 mmol of intermediate C-2, 98.0 mmol of p-toluenesulfonyl chloride, and 98.0 mmol of triethylamine.

[0038] In step S4, the molar ratio of intermediate C-3 to hydroquinone is (0.5 to 1.5):1 (for example, 1:1), the reaction time is 48 - 72 hours (for example, 2 days, that is, 48 hours), and the reaction temperature is 100 - 120 °C (for example, 100 °C); the protective gas is selected from one of nitrogen and argon, for example, nitrogen; the organic solvent is selected from at least one of acetonitrile, acetone, and N,N-dimethylformamide (such as one), for example, N,N-dimethylformamide. Among them, for every 325 mL of organic solvent (such as N,N-dimethylformamide), there are 13.1 mmol of intermediate C-3, 13.1 mmol of hydroquinone, and 65.4 mmol of cesium carbonate.

[0039] Another object of the present invention is to provide a method for regulating the solid-state luminescence of the aforementioned crown ether derivatives. This method regulates the solid-state luminescence properties of the crown ether derivatives by utilizing the difference in the degree of molecular conjugation of the compounds, achieving an enhancement in luminescence intensity and a red shift in the emission wavelength, where:

[0040] As the degree of molecular conjugation of the crown ether derivatives increases, the luminescence intensity of the crown ether derivatives gradually increases, and the fluorescence quantum yield gradually increases;

[0041] As the degree of molecular conjugation of the crown ether derivatives increases, the emission wavelength of the crown ether derivatives gradually redshifts.

[0042] Among them, the aforementioned crown ether derivatives have an adjustable conjugated structure, and this conjugated structure affects their luminescence performance.

[0043] In addition, the aforementioned crown ether derivatives can be applied in solid-state luminescent materials.

[0044] Compared with the prior art, the present invention has significant advantages: First, the synthesis processes of the three crown ether derivatives provided by the present invention are simple, require low equipment requirements, have high conversion rates, and single crystal structures of the corresponding ones have been successfully obtained; Second, these three crown ether derivatives exhibit excellent luminescence properties in the solid state, and their solid-state luminescence properties can also be effectively regulated by adjusting the degree of molecular conjugation, achieving enhanced luminescence and a red shift in the emission wavelength; Finally, the molecular structure design of this type of derivative enables its luminescence characteristics to effectively avoid the interference of the flow characteristics in the solution phase and solvent molecules, thereby broadening the application scope of crown ethers in the field of solid-state luminescent materials. Description of the Drawings

[0045] Figure 1 It is the synthesis route diagram of crown ether derivative A in Example 1;

[0046] Figure 2 It is the nuclear magnetic resonance hydrogen spectrum diagram of crown ether derivative A in Example 1;

[0047] Figure 3Mass spectrum of crown ether derivative A in Example 1;

[0048] Figure 4 Single crystal structure diagram of crown ether derivative A in Example 1;

[0049] Figure 5 Synthesis route diagram of crown ether derivative B in Example 2;

[0050] Figure 6 1H NMR spectrum of crown ether derivative B in Example 2;

[0051] Figure 7 Mass spectrum of crown ether derivative B in Example 2;

[0052] Figure 8 Single crystal structure diagram of crown ether derivative B in Example 2;

[0053] Figure 9 Synthesis route diagram of crown ether derivative C in Example 3;

[0054] Figure 10 1H NMR spectrum of crown ether derivative C in Example 3;

[0055] Figure 11 Mass spectrum of crown ether derivative C in Example 3;

[0056] Figure 12 Single crystal structure diagram of crown ether derivative C in Example 3;

[0057] Figure 13 Photoluminescence spectra of crown ether derivatives A, B, and C in the solid state;

[0058] Figure 14 Quantum yield diagrams of crown ether derivatives A, B, and C in the solid state. Detailed implementation manners

[0059] For the convenience of those skilled in the art to understand, the present invention will be further described below in conjunction with embodiments. The content mentioned in the embodiments does not limit the present invention. It should be noted in advance that the following embodiments are completed in the laboratory. Those skilled in the art should understand that the amounts of each component given in the embodiments only represent the ratio relationship between the components, rather than specific limitations.

[0060] Example 1

[0061] The synthesis route of crown ether derivative A in this example is as Figure 1 shown, and specifically includes the following processes:

[0062] 1. Synthesis of compound A-1 (intermediate A-1):

[0063] Weigh triethylene glycol (4.51 g, 30.0 mmol) and p-toluenesulfonyl chloride (1.91 g, 10.0 mmol) successively into a 250 ml round-bottom flask, then add triethylamine (Et3N, 4.12 ml, 30.0 mmol) and 100 mL of dichloromethane. The mixed solution is stirred vigorously at room temperature for 16 hours. After the reaction is completed, the mixed solution is washed 3 times with 50 mL of 0.5 M hydrochloric acid and 50 mL of saturated brine respectively, then dried with anhydrous sodium sulfate for 30 min, filtered, and separated by silica gel column chromatography. The eluent is petroleum ether: ethyl acetate = 1:5 (volume ratio), and concentrated to obtain a yellow oily liquid, which is compound A-1 (2.31 g, 75.8%).

[0064] 2. Synthesis of compound A-2 (intermediate A-2):

[0065] Add compound A-1 (12.9 g, 42.3 mmol), hydroquinone (2.12 g, 19.2 mmol), potassium carbonate (10.6 g, 76.8 mmol) and acetonitrile (280 mL) into a 500 ml round-bottom flask. The reaction mixture is stirred under nitrogen protection for two days at a reaction temperature of 85 °C. After the reaction is completed, it is cooled to room temperature, the mixture is filtered, the acetonitrile is removed by rotary evaporation, and then dichloromethane is added. The organic phase is washed three times with saturated brine solution, and then dried with anhydrous sodium sulfate. Filter, remove dichloromethane by rotary evaporation under reduced pressure to obtain a yellow oily liquid, which is the crude product of compound A-2. This product does not need to be purified and is directly used for the next reaction.

[0066] 3. Synthesis of compound A-3 (intermediate A-3):

[0067] Add the unpurified compound A-2 (19.2 mmol) from the previous step, p-toluenesulfonyl chloride (18.3 g, 96.1 mmol), triethylamine (Et3N, 13.5 ml, 96.1 mmol) and dichloromethane (300 mL) into a round-bottom flask. The reaction mixture is stirred vigorously at room temperature for 16 hours. After the reaction is completed, the organic phase is washed three times with 0.5 M hydrochloric acid and saturated brine solution respectively, and then dried with anhydrous sodium sulfate. Filter, concentrate under reduced pressure and then purify by silica gel column chromatography. The eluent is petroleum ether: ethyl acetate = 1:3 (volume ratio) to obtain a yellow oily product, which is compound A-3 (7.37 g, yield 56.3%).

[0068] 4. Synthesis of crown ether derivative A:

[0069] In a 500 mL three-necked flask, cesium carbonate (20.52 g, 62.5 mmol) and N,N-dimethylformamide (265 mL) were added, and the mixture was heated to 100 °C under nitrogen protection. Then, a mixed solution of compound A-3 (8.52 g, 12.5 mmol) and hydroquinone (1.38 g, 12.5 mmol) in N,N-dimethylformamide (50 mL) was slowly added dropwise to the stirred cesium carbonate suspension over 12 hours. After the addition was completed, the reaction mixture was allowed to react for another 2 days at 100 °C under nitrogen protection. After the reaction was completed, it was cooled to room temperature, the mixture was filtered, N,N-dimethylformamide was removed by rotary evaporation, and then dichloromethane was added. The organic phase was washed three times with saturated saline solution and then dried over anhydrous sodium sulfate. After filtration and concentration under reduced pressure, purification was carried out by silica gel column chromatography, and the eluent was petroleum ether:ethyl acetate = 1:5 (volume ratio) to obtain a white solid product, which was crown ether derivative A (1.93 g, yield 34.4%).

[0070] The characterization data of the 1H NMR spectrum of crown ether derivative A is as Figure 2 shown:

[0071] 1 H NMR (400 MHz, CDCl3, 298 K, ppm): δ 6.75 (s, 8H), 4.02–3.98 (m, 8H), 3.84–3.80 (m, 8H), 3.73 (s, 8H).

[0072] Figure 3 The mass spectrometry test value shows m / z: 471.1992, corresponding to [crown ether derivative A + Na] + .

[0073] Figure 4 The single crystal structure shows that the obtained crown ether derivative A has a good crystal structure, and its relevant parameters are a = 11.0760(15), b = 5.0885(6), c = 19.916(3), α = 90, β = 94.749(4), γ = 90 respectively.

[0074] Example 2

[0075] The synthetic route of crown ether derivative B in this example is as Figure 5 shown, and specifically includes the following process:

[0076] 1. Synthesis of compound B-1 (intermediate B-1):

[0077] Weigh triethylene glycol (4.51 g, 30.0 mmol) and p-toluenesulfonyl chloride (1.91 g, 10.0 mmol) successively and place them in a 250 ml round-bottom flask. Then add triethylamine (Et3N, 4.12 ml, 30.0 mmol) and 100 mL of dichloromethane. The mixed solution is stirred vigorously at room temperature for 16 hours. After the reaction is completed, the mixed solution is washed 3 times with 50 mL of 0.5 M hydrochloric acid and 50 mL of saturated brine respectively, then dried with anhydrous sodium sulfate for 30 min, filtered, separated by silica gel column chromatography, and the eluent is petroleum ether:ethyl acetate = 1:5 (volume ratio). After concentration, a yellow oily liquid is obtained, which is compound B-1 (2.31 g, 75.8%).

[0078] 2. Synthesis of compound B-2 (intermediate B-2):

[0079] Add compound B-1 (13.2 g, 43.5 mmol), 1,4-dihydroxynaphthalene (3.17 g, 19.8 mmol), potassium carbonate (10.9 g, 79.2 mmol) and acetonitrile (280 mL) to a 500 ml round-bottom flask. The reaction mixture is stirred under nitrogen protection for two days at a reaction temperature of 85 °C. After the reaction is completed, it is cooled to room temperature, the mixture is filtered, the acetonitrile is removed by rotary evaporation, and then dichloromethane is added. The organic phase is washed three times with saturated brine solution, and then dried with anhydrous sodium sulfate. After filtration, dichloromethane is removed by rotary evaporation under reduced pressure to obtain a yellow oily liquid, which is the crude product of compound B-2. This product does not need to be purified and is directly used for the next reaction.

[0080] 3. Synthesis of compound B-3 (intermediate B-3):

[0081] Add the unpurified compound B-2 (19.8 mmol) from the previous step, p-toluenesulfonyl chloride (19.1 g, 99.0 mmol), triethylamine (Et3N, 14.1 ml, 99.0 mmol) and dichloromethane (300 mL) to a round-bottom flask. The reaction mixture is stirred vigorously at room temperature for 16 hours. After the reaction is completed, the organic phase is washed three times with 0.5 M hydrochloric acid and saturated brine solution respectively, and then dried with anhydrous sodium sulfate. After filtration, it is concentrated under reduced pressure and purified by silica gel column chromatography. The eluent is petroleum ether:ethyl acetate = 1:3 (volume ratio) to obtain a yellow oily product, which is compound B-3 (7.71 g, yield 53.2%).

[0082] 4. Synthesis of crown ether derivative B:

[0083] In a 500 mL three-necked flask, cesium carbonate (19.42 g, 59.1 mmol) and N,N-dimethylformamide (250 mL) were added, and the mixture was heated to 100 °C under nitrogen protection. Subsequently, a mixed solution of compound B-3 (8.65 g, 11.8 mmol) and hydroquinone (1.31 g, 11.8 mmol) in N,N-dimethylformamide (50 mL) was slowly added dropwise to the stirred cesium carbonate suspension over 12 hours. After the addition was complete, the reaction mixture was continued to react for 2 days at 100 °C under nitrogen protection. After the reaction was completed, it was cooled to room temperature, the mixture was filtered, N,N-dimethylformamide was removed by rotary evaporation, and then dichloromethane was added. The organic phase was washed three times with saturated saline solution and then dried over anhydrous sodium sulfate. After filtration and concentration under reduced pressure, purification was carried out by silica gel column chromatography, and the eluent was petroleum ether:ethyl acetate = 1:5 (volume ratio) to obtain a white solid product, which was crown ether derivative B (1.79 g, yield 30.5%).

[0084] The characterization data of the 1H NMR spectrum of crown ether derivative B are as Figure 6 follows:

[0085] 1 H NMR (400 MHz, CDCl3, 298 K, ppm): δ 8.24 (dd, J = 6.4, 3.3 Hz, 2H), 7.46 (dd, J = 6.4, 3.3 Hz, 2H), 6.61 (s, 2H), 6.53 (s, 4H), 4.22–4.17 (m, 4H), 4.00–3.96 (m, 4H), 3.81–3.73 (m, 16H).

[0086] Figure 7 The mass spectrometry test value shows m / z: 521.2149, corresponding to [crown ether derivative B + Na] + .

[0087] Figure 8 The single crystal structure shows that the obtained crown ether derivative B has a good crystal structure, and its relevant parameters are a = 9.97900, b = 10.75800, c = 13.80200, α = 69.6200, β = 85.3700, γ = 66.4100 respectively.

[0088] Example 3

[0089] The synthesis route of crown ether derivative C in this example is as Figure 9 follows, and specifically includes the following processes:

[0090] 1. Synthesis of compound C-1 (intermediate C-1):

[0091] Weigh triethylene glycol (4.51 g, 30.0 mmol) and p-toluenesulfonyl chloride (1.91 g, 10.0 mmol) successively and place them in a 250 ml round-bottom flask. Then add triethylamine (Et3N, 4.12 ml, 30.0 mmol) and 100 mL of dichloromethane. The mixed solution is stirred vigorously at room temperature for 16 hours. After the reaction is completed, the mixed solution is washed 3 times with 50 mL of 0.5 M hydrochloric acid and 50 mL of saturated brine respectively, then dried with anhydrous sodium sulfate for 30 min, filtered, separated by silica gel column chromatography, and the eluent is petroleum ether:ethyl acetate = 1:5 (volume ratio). Concentrate to obtain a yellow oily liquid, which is compound C-1 (2.31 g, 75.8%).

[0092] 2. Synthesis of compound C-2 (intermediate C-2):

[0093] Add compound C-1 (13.1 g, 43.1 mmol), 1,4-dihydroxyanthracene (4.12 g, 19.6 mmol), potassium carbonate (10.8 g, 78.4 mmol) and acetonitrile (280 mL) to a 500 ml round-bottom flask. The reaction mixture is stirred under nitrogen protection for two days at a reaction temperature of 85 °C. After the reaction is completed, cool to room temperature, filter the mixture, rotary evaporate to remove acetonitrile, and then add dichloromethane. The organic phase is washed three times with saturated brine solution and then dried with anhydrous sodium sulfate. Filter, rotary evaporate under reduced pressure to remove dichloromethane to obtain a yellow oily liquid, which is the crude product of compound C-2. This product does not need to be purified and is directly used for the next reaction.

[0094] 3. Synthesis of compound C-3 (intermediate C-3):

[0095] Add the unpurified compound C-2 (19.6 mmol) from the previous step, p-toluenesulfonyl chloride (18.7 g, 98.0 mmol), triethylamine (Et3N, 13.8 ml, 98.0 mmol) and dichloromethane (300 mL) to a round-bottom flask. The reaction mixture is stirred vigorously at room temperature for 16 hours. After the reaction is completed, the organic phase is washed three times with 0.5 M hydrochloric acid and saturated brine solution respectively, and then dried with anhydrous sodium sulfate. Filter, concentrate under reduced pressure and then purify by silica gel column chromatography. The eluent is petroleum ether:ethyl acetate = 1:3 (volume ratio) to obtain a yellow oily product, which is compound C-3 (7.83 g, yield 51.1%).

[0096] 4. Synthesis of crown ether derivative C:

[0097] In a 500 mL three-necked flask, cesium carbonate (21.5 g, 65.4 mmol) and N,N-dimethylformamide (275 mL) were added, and the mixture was heated to 100 °C under nitrogen protection. Then, a mixed solution of compound C-3 (10.2 g, 13.1 mmol) and hydroquinone (1.44 g, 13.1 mmol) in N,N-dimethylformamide (50 mL) was slowly added dropwise to the stirred cesium carbonate suspension over 12 hours. After the addition was complete, the reaction mixture was allowed to react for another 2 days at 100 °C under nitrogen protection. After the reaction was completed, it was cooled to room temperature, the mixture was filtered, N,N-dimethylformamide was removed by rotary evaporation, and then dichloromethane was added. The organic phase was washed three times with saturated sodium chloride solution and then dried over anhydrous sodium sulfate. After filtration and concentration under reduced pressure, purification was carried out by silica gel column chromatography, and the eluent was petroleum ether:ethyl acetate = 1:5 (volume ratio) to obtain a yellow solid product, which was crown ether derivative C (1.97 g, yield 27.4%).

[0098] The characterization data of the 1H NMR spectrum of crown ether derivative C are as Figure 10 shown:

[0099] 1 H NMR (400 MHz, CDCl3, 298 K, ppm): δ 8.79 (s, 2H), 8.02 (dd, J = 6.3, 3.1 Hz, 2H), 7.45 (dd, J = 6.5, 3.0 Hz, 2H), 6.52 (s, 2H), 6.46 (s, 4H), 4.27 (t, J = 4.7 Hz, 4H), 4.07–4.03 (m, 4H), 3.83 (d, J = 2.4 Hz, 4H), 3.75 (s, 12H).

[0100] Figure 11 The mass spectrometry test value shows m / z: 571.2301, corresponding to [crown ether derivative C + Na] + .

[0101] Figure 12 The single crystal structure shows that the obtained crown ether derivative C has a good crystal structure, and its relevant parameters are a = 10.106(10), b = 11.274(10), c = 13.312(11), α = 108.12 (2), β = 99.56 (3), γ = 98.13 (3).

[0102] Figure 13 are the photoluminescence spectra of crown ether derivatives A, B, and C in the solid state. It can be seen from the figure that the three crown ether derivatives show an obvious red shift of solid-state luminescence, and their maximum emission peaks are located at 320 nm, 400 nm, and 468 nm, respectively.

[0103] Figure 14 It is the quantum yield diagram of crown ether derivatives A, B, and C in the solid state. It can be seen from the figure that the three crown ether derivatives show obvious solid-state luminescence enhancement phenomena, and their fluorescence quantum yields are 2.76%, 15.40%, and 21.13% respectively.

[0104] In summary, through reasonable molecular structure design, the present invention successfully obtains three crown ether derivatives A, B, and C. Compared with the prior art, the method provided by the present invention has simple synthesis, low equipment requirements, high conversion rate, and single crystal structures of the corresponding compounds are obtained. At the same time, the solid-state luminescence properties of crown ether derivatives can be regulated by the difference in the conjugation degree of compound molecules, realizing luminescence enhancement and red shift of the emission wavelength.

[0105] The above embodiments are the preferred implementation schemes of the present invention. In addition, the present invention can also be implemented in other ways. Any obvious replacement without departing from the concept of the technical solution of the present invention is within the protection scope of the present invention.

[0106] Finally, it should be emphasized that in order to make it more convenient for those of ordinary skill in the art to understand the improvements of the present invention over the prior art, some descriptions of the present invention have been simplified, and for the sake of clarity, some other elements have also been omitted from this application document. Those skilled in the art should be aware that these omitted elements may also constitute the content of the present invention.

Claims

1. A crown ether derivative, characterized in that: Selected from crown ether derivatives A, B or C, the derivative has a specific conjugated structure, wherein the structural formula of crown ether derivative A is shown in formula A, the structural formula of crown ether derivative B is shown in formula B, and the structural formula of crown ether derivative C is shown in formula C:

2. The crown ether derivative according to claim 1, characterized in that The crown ether derivative A is prepared by the following steps: S1. Synthesis of intermediate A-1: ​​triethylene glycol, p-toluenesulfonyl chloride and triethylamine are added to an organic solvent for reaction to obtain intermediate A-1; S2. Synthesis of intermediate A-2: In an organic solvent, add intermediate A-1, hydroquinone and potassium carbonate under a protective gas environment to react to obtain intermediate A-2; S3, synthesis of intermediate A-3: In an organic solvent, add intermediate A-2, p-toluenesulfonyl chloride and triethylamine to react to obtain intermediate A-3; S4. Synthesis of crown ether derivative A: In an organic solvent, intermediate A-3, hydroquinone and cesium carbonate are added under a protective gas environment to react to obtain crown ether derivative A.

3. The crown ether derivative according to claim 2, characterized in that: In step S1, every 100 mL of organic solvent corresponds to 30.0 mmol of triethylene glycol, 10.0 mmol of p-toluenesulfonyl chloride and 30.0 mmol of triethylamine, and the organic solvent is selected from at least one of 1,2-dichloroethane, chloroform and dichloromethane; In step S2, every 280 mL of organic solvent corresponds to 42.3 mmol of intermediate A-1, 19.2 mmol of hydroquinone and 76.8 mmol of potassium carbonate, the organic solvent is selected from at least one of tetrahydrofuran, acetonitrile and acetone, and the protective gas is selected from one of nitrogen and argon; In step S3, every 300 mL of organic solvent corresponds to 19.2 mmol of intermediate A-2, 96.1 mmol of p-toluenesulfonyl chloride and 96.1 mmol of triethylamine, and the organic solvent is selected from at least one of 1,2-dichloroethane, chloroform and dichloromethane; In step S4, every 315 mL of organic solvent corresponds to 12.5 mmol of intermediate A-3, 12.5 mmol of hydroquinone and 62.5 mmol of cesium carbonate, the organic solvent is selected from at least one of acetonitrile, acetone and N,N-dimethylformamide, and the protective gas is selected from one of nitrogen and argon.

4. The crown ether derivative according to claim 1, characterized in that The crown ether derivative B is prepared by the following steps: S1. Synthesis of intermediate B-1: triethylene glycol, p-toluenesulfonyl chloride and triethylamine are added to an organic solvent for reaction to obtain intermediate B-1; S2. Synthesis of intermediate B-2: In an organic solvent, intermediate B-1, 1,4-dihydroxynaphthalene and potassium carbonate are added under a protective gas environment to react to obtain intermediate B-2; S3, synthesis of intermediate B-3: In an organic solvent, add intermediate B-2, p-toluenesulfonyl chloride and triethylamine to react to obtain intermediate B-3; S4. Synthesis of crown ether derivative B: In an organic solvent, add intermediate B-3, hydroquinone and cesium carbonate under a protective gas environment to react to obtain crown ether derivative B.

5. The crown ether derivative according to claim 4, characterized in that: In step S1, every 100 mL of organic solvent corresponds to 30.0 mmol of triethylene glycol, 10.0 mmol of p-toluenesulfonyl chloride and 30.0 mmol of triethylamine, and the organic solvent is selected from at least one of 1,2-dichloroethane, chloroform and dichloromethane; In step S2, every 280 mL of organic solvent corresponds to 43.5 mmol of intermediate B-1, 19.8 mmol of 1,4-dihydroxynaphthalene and 79.2 mmol of potassium carbonate, the organic solvent is selected from at least one of tetrahydrofuran, acetonitrile and acetone, and the protective gas is selected from one of nitrogen and argon; In step S3, every 300 mL of organic solvent corresponds to 19.8 mmol of intermediate B-2, 99.0 mmol of p-toluenesulfonyl chloride and 99.0 mmol of triethylamine, and the organic solvent is selected from at least one of 1,2-dichloroethane, chloroform and dichloromethane; In step S4, every 300 mL of organic solvent corresponds to 11.8 mmol of intermediate B-3, 11.8 mmol of hydroquinone and 59.1 mmol of cesium carbonate, the organic solvent is selected from at least one of acetonitrile, acetone and N,N-dimethylformamide, and the protective gas is selected from one of nitrogen and argon.

6. The crown ether derivative according to claim 1, characterized in that The crown ether derivative C is prepared by the following steps: S1. Synthesis of intermediate C-1: triethylene glycol, p-toluenesulfonyl chloride and triethylamine are added to an organic solvent for reaction to obtain intermediate C-1; S2. Synthesis of intermediate C-2: In an organic solvent, intermediate C-1, 1,4-dihydroxyanthracene and potassium carbonate are added under a protective gas environment to react to obtain intermediate C-2; S3, synthesis of intermediate C-3: In an organic solvent, add intermediate C-2, p-toluenesulfonyl chloride and triethylamine to react to obtain intermediate C-3; S4. Synthesis of crown ether derivative C: In an organic solvent, add intermediate C-3, hydroquinone and cesium carbonate under a protective gas environment to react to obtain crown ether derivative C.

7. The crown ether derivative according to claim 6, characterized in that: In step S1, every 100 mL of organic solvent corresponds to 30.0 mmol of triethylene glycol, 10.0 mmol of p-toluenesulfonyl chloride and 30.0 mmol of triethylamine, and the organic solvent is selected from at least one of 1,2-dichloroethane, chloroform and dichloromethane; In step S2, every 280 mL of organic solvent corresponds to 43.1 mmol of intermediate C-1, 19.6 mmol of 1,4-dihydroxyanthracene and 78.4 mmol of potassium carbonate, the organic solvent is selected from at least one of tetrahydrofuran, acetonitrile and acetone, and the protective gas is selected from one of nitrogen and argon; In step S3, every 300 mL of organic solvent corresponds to 19.6 mmol of intermediate C-2, 98.0 mmol of p-toluenesulfonyl chloride and 98.0 mmol of triethylamine, and the organic solvent is selected from at least one of 1,2-dichloroethane, chloroform and dichloromethane; In step S4, every 325 mL of organic solvent corresponds to 13.1 mmol of intermediate C-3, 13.1 mmol of hydroquinone and 65.4 mmol of cesium carbonate, the organic solvent is selected from at least one of acetonitrile, acetone and N,N-dimethylformamide, and the protective gas is selected from one of nitrogen and argon.

8. The method for controlling solid-state luminescence of the crown ether derivative according to claim 1, characterized in that: By utilizing the difference in the degree of conjugation of the compound molecules, the solid-state luminescence properties of the crown ether derivatives are regulated to achieve enhanced luminescence intensity and red shift of the emission wavelength, wherein: With the increase of the molecular conjugation degree of crown ether derivatives, the luminescence intensity of crown ether derivatives gradually increases, and the fluorescence quantum yield gradually increases; As the degree of conjugation of crown ether derivative molecules increases, the emission wavelength of crown ether derivatives gradually red-shifts.

9. Use of the crown ether derivative according to claim 1 in solid-state luminescent materials.

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