A method for preparing a circularly polarized luminescent thermally activated delayed fluorescence material

Abstract

The application relates to a preparation method of circularly polarized luminescent thermally activated delayed fluorescence material, and the circularly polarized luminescent thermally activated delayed fluorescence material is non-toxic and harmless, can realize the effect of thermally activated delayed fluorescence through self-assembly by aggregation in a mixed solution of an aqueous phase and an organic phase, and can be used for devices and cell imaging. After phagocytosis of HeLa cells, cell imaging can be realized through time-resolved means, so that a more complete effect of imaging is realized, and a clearer imaging effect is ensured; the thermally activated delayed fluorescence material can realize the effect of fluorescence-phosphorescence conversion through oxygen removal in a solution. The material structure is controllable, the property is stable, the performance of phosphorescent material and thermally activated delayed fluorescence is combined, more complete and clear time-resolved imaging is realized, and a research foundation is provided for in-depth research of biological imaging.

Description

TECHNICAL FIELD

[0001] The application relates to a preparation method of circularly polarized luminescent thermally activated delayed fluorescence material. BACKGROUND

[0002] Circularly polarized luminescence (CPL) as one of the most important properties of chiral materials reflects the information of the excited state of chiral luminescent systems, and is expected to provide core technical support for detection, sensing, biological imaging, new optoelectronic devices and other fields. For organic chiral luminescent materials, thermally activated delayed fluorescence (TADF) materials can convert non-radiative triplet states into radiative singlet states in the presence of a small singlet-triplet split, and circularly polarized luminescence (CPL) materials with TADF characteristics have great potential in terms of high circular polarization asymmetry factor |gPL|.

[0003] In recent years, organic chiral materials based on molecular assembly to produce circularly polarized luminescence (CPL) have developed rapidly. However, due to the lack of efficient and universal methods to obtain single mirror image luminescence at the supramolecular and material levels, the CPL intensity is generally weak and difficult to meet the actual needs. At present, the CPL signal of the organic material system is still weak as a whole, and lacks precise control means, which leads to the inability to realize complete and clear time-resolved imaging.

[0004] Therefore, the current delayed fluorescence material and the preparation method thereof still need to be further improved. SUMMARY

[0005] The technical problem to be solved by the application is to provide a preparation method of circularly polarized luminescent thermally activated delayed fluorescence material which can combine the performance of phosphorescent material and thermally activated delayed fluorescence to realize more complete and clear time-resolved imaging.

[0006] The technical scheme adopted by the application to solve the above technical problem is:

[0007] A preparation method of circularly polarized luminescent thermally activated delayed fluorescence material, the structural formula of the circularly polarized luminescent thermally activated delayed fluorescence material is:

[0008]

[0009] Wherein, X is one of H, O and S, Y is a -CH3 group.

[0010] The target product of the circularly polarized luminescent thermally activated delayed fluorescence material is obtained by first carrying out a nucleophilic substitution reaction with an amine derivative and then carrying out a coupling reaction with a chiral molecule, with 4,4'-dibromodiphenyl sulfone as the mother nucleus.

[0011] Preferably, the amine derivative is phenothiazine, phenoxazine or acridine.

[0012] Preferably, the preparation method of the circularly polarized luminescent thermally activated delayed fluorescence material is:

[0013] (1) Preparation of compound 1

[0014] Dissolve 2.0-3.0 g of phenothiazine in DMF (5 mL), add 0.1-1.0 g of sodium hydride, stir under nitrogen protection for 15-30 min, then add 1.0-3.0 g of 4,4'-dibromodiphenyl sulfone, and react at 100-140℃ for 24-48 h;

[0015]

[0016] After the reaction is completed, the temperature is lowered to room temperature, water is extracted at least twice, the organic phase solution is collected, anhydrous sodium sulfate is added to absorb excess water, the supernatant is obtained by filtration, and the organic solvent is removed by rotary evaporation to obtain a yellow solid, which is compound 1;

[0017] (2) Preparation of compound 2

[0018] Dissolve compound 1 in 10-25 mL of toluene, add 1.0-2.0 g of 1-phenyl-1,2,3,4-tetrahydroisoquinoline, 0.1-0.5 g of Pd2dba3, and 2.0-3.0 g of potassium tert-butoxide, stir under nitrogen protection for 5-15 min, heat to 80-120℃, and react for 24-48 h;

[0019]

[0020] After the reaction is completed, the temperature is lowered to room temperature, water is extracted at least twice, the organic phase solution is collected, anhydrous sodium sulfate is added to absorb excess water, the supernatant is obtained by filtration, and the organic solvent is removed by rotary evaporation to obtain a yellow solid, which is compound 2.

[0021] Preferably, the 1-phenyl-1,2,3,4-tetrahydroisoquinoline in the above step (2) is R-1-phenyl-1,2,3,4-tetrahydroisoquinoline, and the structural formula of the compound 2 is

[0022]

[0023] Preferably, the 1-phenyl-1,2,3,4-tetrahydroisoquinoline in the above step (2) is S-1-phenyl-1,2,3,4-tetrahydroisoquinoline, and the structural formula of the compound 2 is

[0024]

[0025] Preferably, the preparation method of the circularly polarized luminescent thermally activated delayed fluorescence material is:

[0026] (1) Preparation of compound 1

[0027] Dissolve 1.8 g acridine in DMF (5 mL), add 500 mg sodium hydride, stir for 15 min under nitrogen protection, then add 1.5 g 4,4'-dibromodiphenyl sulfone, and react at 120 °C for 24 h.

[0028]

[0029] After the reaction was completed, the temperature was allowed to drop to room temperature. The solution was extracted with water at least twice, and the organic phase solution was collected. Anhydrous sodium sulfate was added to absorb the excess water. The solution was filtered to obtain the supernatant. The organic solvent was evaporated to obtain a yellow solid, which is compound 1.

[0030] (2) Preparation of compound 2

[0031] Compound 1 was dissolved in 15 mL of toluene, and 1.0 g of S-1-phenyl-1,2,3,4-tetrahydroisoquinoline, 300 mg of Pd2dba3, and 3.0 g of potassium tert-butoxide were added. The mixture was stirred for 5 min under nitrogen protection and then heated to 110 °C for 24 h.

[0032]

[0033] After the reaction was completed, the temperature was allowed to drop to room temperature. The solution was extracted with water at least twice, and the organic phase solution was collected. Anhydrous sodium sulfate was added to absorb the excess water. The supernatant was filtered to obtain the clear liquid. The organic solvent was evaporated by rotary evaporation, and the yellow solid obtained by column chromatography was the target product compound 2.

[0034] Preferably, the preparation method of the circularly polarized luminescent thermally activated delayed fluorescence material is as follows:

[0035] (1) Preparation of compound 1

[0036] Dissolve 1.8 g acridine in DMF (5 mL), add 500 mg sodium hydride, stir for 15 min under nitrogen protection, then add 1.5 g 4,4'-dibromodiphenyl sulfone, and react at 120 °C for 24 h.

[0037]

[0038] After the reaction was completed, the temperature was allowed to drop to room temperature. The solution was extracted with water at least twice, and the organic phase solution was collected. Anhydrous sodium sulfate was added to absorb the excess water. The solution was filtered to obtain the supernatant. The organic solvent was evaporated to obtain a yellow solid, which is compound 1.

[0039] (2) Preparation of compound 2

[0040] Compound 1 is dissolved in 15 mL of toluene, 1.0 g of R-1-phenyl-1,2,3,4-tetrahydroisoquinoline, 300 mg of Pd2dba3, 3.0 g of potassium tert-butoxide are added, stirred for 5 min under nitrogen protection, heated to 110 DEG C and reacted for 24 h;

[0041]

[0042] After the reaction is completed, the temperature is reduced to room temperature, water is extracted at least twice, the organic phase solution is collected, anhydrous sodium sulfate is added to the organic phase solution to remove excess water, the upper clear liquid is filtered, the organic solvent is distilled off, and the yellow solid is obtained by column chromatography.

[0043] Compared with the prior art, the advantages of the present application are:

[0044] (1) The circularly polarized luminescent thermally activated delayed fluorescence material of the present application is non-toxic and harmless, can realize the effect of thermally activated delayed fluorescence by self-assembly through aggregation in a mixed solution of an aqueous phase and an organic phase, and can be used in devices and cell imaging. After phagocytosis by HeLa cells, time-resolved means can be used to realize more complete cell imaging, so as to ensure clearer imaging effect;

[0045] (2) The circularly polarized luminescent thermally activated delayed fluorescence material of the present application can realize the effect of fluorescence-phosphorescence conversion in a solution by means of oxygen removal (can be systemically). The material structure is controllable and the properties are stable. The performance of phosphorescent material and thermally activated delayed fluorescence is combined to realize more complete and clear time-resolved imaging, which provides a research basis for in-depth study of biological imaging;

[0046] (3) The circularly polarized luminescent thermally activated delayed fluorescence material prepared by the present application provides a self-assembly functional chiral assembly system, which can effectively regulate the TADF properties in an organic solvent / water reagent, so as to realize the effect of coordination of organic material self-assembly and TADF;

[0047] (4) The circularly polarized luminescent thermally activated delayed fluorescence material of the present application has good biocompatibility, low toxicity, and the raw materials are cheap and easy to obtain. The synthesis route is simple and easy to realize industrialized production. BRIEF DESCRIPTION OF DRAWINGS

[0048] Figure 1 The 1HNMR spectrum of the circularly polarized luminescent thermally activated delayed fluorescence material obtained in Example 1 of the present application is shown in the figure;

[0049] Figure 2 The 1HNMR spectrum of the circularly polarized luminescent thermally activated delayed fluorescence material obtained in Example 2 of the present application is shown in the figure;

[0050] Figure 3The fluorescence diagram of the circularly polarized luminescent thermally activated delayed fluorescence material of Example 1 of the present application in different solvents under 365 nm laser irradiation;

[0051] Figure 4 The CIE diagram of the circularly polarized luminescent thermally activated delayed fluorescence material of Example 1 of the present application in different solvents;

[0052] Figure 5 The lifetime fitting diagram of the circularly polarized luminescent thermally activated delayed fluorescence material of Example 1 of the present application in different solvents under temperature change test. DETAILED DESCRIPTION

[0053] The present application will be further described in detail below with reference to the accompanying drawings.

[0054] Example 1:

[0055] The structural formula of the circularly polarized luminescent thermally activated delayed fluorescence material of the present example is:

[0056]

[0057] The preparation method of the circularly polarized luminescent thermally activated delayed fluorescence material of the present example is:

[0058] (1) Preparation of compound 1

[0059] Dissolve 2.0 g of phenothiazine in DMF (5 mL), add 500 mg of sodium hydride, stir for 15 min under nitrogen protection, then add 1.5 g of 4,4'-dibromodiphenyl sulfone, and react at 120℃ for 24 h;

[0060]

[0061] After the reaction is completed, when the temperature drops to room temperature, extract with water twice, collect the organic phase solution, add anhydrous sodium sulfate to the solution to absorb excess water, filter to obtain the supernatant, and rotary evaporate the organic solvent to obtain a yellow solid, which is compound 1;

[0062] (2) Preparation of compound 2

[0063] Dissolve compound 1 in 15 mL of toluene, add 1.0 of S-1-phenyl-1,2,3,4-tetrahydroisoquinoline, 300 mg of Pd2dba3, and 3.0 g of potassium tert-butoxide, stir for 5 min under nitrogen protection, heat to 110℃ and react for 24 h;

[0064]

[0065] After the reaction, when the temperature drops to room temperature, extract twice with water, collect the organic phase solution, add anhydrous sodium sulfate to absorb excess water, filter to obtain the supernatant, rotary evaporate the organic solvent, and pass through a column to obtain a yellow solid, which is the target product compound 2.

[0066] Figure 1 The target product obtained in this example is 1 HNMR spectrum,

[0067] 1 H NMR (400 MHz, DMSO-d6) δ 7.81-7.75 (m, 2H), 7.70-7.64 (m, 2H), 7.57-7.53 (m, 1H), 7.46 (dd, J = 7.7, 1.5 Hz, 2H), 7.35-7.08 (m, 16H), 6.92 (d, J = 9.2 Hz, 2H), 6.14 (s, 1H), 3.91-3.83 (m, 1H), 3.49 (dt, J = 10.9, 5.5 Hz, 1H), 3.02-2.94 (m, 1H), 2.85 (td, J = 10.4, 5.4 Hz, 1H).

[0068] Example 2:

[0069] The structural formula of the circularly polarized luminescent thermally activated delayed fluorescence material of this example is:

[0070]

[0071] The preparation method of the circularly polarized luminescent thermally activated delayed fluorescence material of this example is:

[0072] (1) Preparation of compound 1

[0073] Dissolve 2.0 g of phenothiazine in DMF (5 mL), add 500 mg of sodium hydride, stir for 15 min under nitrogen protection, then add 1.5 g of 4,4'-dibromodiphenyl sulfone, and react at 120°C for 24 h;

[0074]

[0075] After the reaction, when the temperature drops to room temperature, extract twice with water, collect the organic phase solution, add anhydrous sodium sulfate to absorb excess water, filter to obtain the supernatant, rotary evaporate the organic solvent, and pass through a column to obtain a yellow solid, which is the target product compound 2.

[0076] (2) Preparation of compound 2

[0077] Compound 1 was dissolved in 15 mL of toluene, 1.0 of R-1-phenyl-1,2,3,4-tetrahydroisoquinoline, 300 mg of Pd2dba3, 3.0 g of potassium tert-butoxide were added, stirred for 5 min under nitrogen protection, heated to 110°C for 24 h;

[0078]

[0079] After the reaction was completed, the temperature was reduced to room temperature, extracted with water twice, collected the organic phase solution, added anhydrous sodium sulfate to the solution to remove excess water, filtered to obtain the supernatant, rotary evaporated the organic solvent, and column chromatography to obtain the yellow solid as the target product compound 2.

[0080] Figure 2 The target product obtained in this example is 1 HNMR spectrum,

[0081] 1 H NMR (400 MHz, DMSO-d6) δ 7.82-7.74 (m, 2H), 7.70-7.63 (m, 2H), 7.58-7.51 (m, 1H), 7.46 (dd, J = 7.7, 1.5 Hz, 2H), 7.35-7.10 (m, 16H), 6.92 (d, J = 9.1 Hz, 2H), 6.14 (s, 1H), 3.87 (dd, J = 10.9, 5.5 Hz, 1H), 3.49 (dt, J = 10.9, 5.5 Hz, 1H), 3.02-2.94 (m, 1H), 2.90-2.81 (m, 1H).

[0082] Example 3:

[0083] The structural formula of the circularly polarized luminescent thermally activated delayed fluorescence material of this example is:

[0084]

[0085] The preparation method of the circularly polarized luminescent thermally activated delayed fluorescence material of this example is:

[0086] (1) Preparation of compound 1

[0087] 1.8 g of acridine was dissolved in DMF (5 mL), 500 mg of sodium hydride was added, stirred for 15 min under nitrogen protection, then 1.5 g of 4,4'-dibromodiphenyl sulfone was added, and reacted at 120°C for 24 h;

[0088]

[0089] After the reaction, when the temperature drops to room temperature, extract twice with water, collect the organic phase solution, add anhydrous sodium sulfate to absorb excess water, filter to obtain the supernatant, rotary evaporate the organic solvent, and obtain yellow solid, which is compound 1.

[0090] (2) Preparation of compound 2

[0091] Compound 1 is dissolved in 15 mL of toluene, 1.0 g of S-1-phenyl-1,2,3,4-tetrahydroisoquinoline, 300 mg of Pd2dba3, and 3.0 g of potassium tert-butoxide are added, stirred for 5 min under nitrogen protection, heated to 110°C and reacted for 24 h.

[0092]

[0093] After the reaction, when the temperature drops to room temperature, extract twice with water, collect the organic phase solution, add anhydrous sodium sulfate to absorb excess water, filter to obtain the supernatant, rotary evaporate the organic solvent, and obtain yellow solid, which is compound 2.

[0094] Example 4:

[0095] The structural formula of the circularly polarized luminescent thermally activated delayed fluorescence material of the present embodiment is:

[0096]

[0097] The preparation method of the circularly polarized luminescent thermally activated delayed fluorescence material of the present embodiment is:

[0098] (1) Preparation of compound 1

[0099] 1.8 g of acridine is dissolved in DMF (5 mL), 500 mg of sodium hydride is added, stirred for 15 min under nitrogen protection, then 1.5 g of 4,4'-dibromodiphenyl sulfone is added, and reacted at 120°C for 24 h.

[0100]

[0101] After the reaction, when the temperature drops to room temperature, extract twice with water, collect the organic phase solution, add anhydrous sodium sulfate to absorb excess water, filter to obtain the supernatant, rotary evaporate the organic solvent, and obtain yellow solid, which is compound 1.

[0102] (2) Preparation of compound 2

[0103] Compound 1 is dissolved in 15 mL of toluene, 1.0 g of R-1-phenyl-1,2,3,4-tetrahydroisoquinoline, 300 mg of Pd2dba3, and 3.0 g of potassium tert-butoxide are added, stirred for 5 min under nitrogen protection, heated to 110°C and reacted for 24 h.

[0104]

[0105] After the reaction, when the temperature dropped to room temperature, the organic phase solution was extracted twice with water, anhydrous sodium sulfate was added to the solution to absorb excess water, the upper clear liquid was filtered, the organic solvent was distilled off, and the yellow solid was obtained by column chromatography. The target product compound 2 was obtained.

[0106] The prepared product was subjected to performance detection.

[0107] (1) Fluorescence images of circularly polarized luminescence thermally activated delayed fluorescence materials in different solvents

[0108] The fluorescent material prepared in Example 2 was diluted with THF to 10 -5 M concentration, and then added to a mixed solvent of THF and water in different proportions (water volume concentrations were 0%, 50%, 80%, 85%, and 95%), and dropped into a fluorescence cuvette. Under 365 nm laser irradiation, the color change of the circularly polarized luminescence thermally activated delayed fluorescence material was observed. As shown in Figure 3 , 4 The material changed the fluorescence color visible to the naked eye from a low polarity solvent to a high polarity solvent, indicating that the material molecules underwent charge transfer in the solvent, and had the property of thermally activated delayed fluorescence.

[0109] (2) Variable temperature test of circularly polarized luminescence thermally activated delayed fluorescence material

[0110] The fluorescent material prepared in Example 2 was diluted (diluted with THF solution) to 10 -5 M concentration was added to a fluorescence cuvette, liquid nitrogen was added in a low temperature device to cool to 77 K, and the fluorescence color change of the circularly polarized luminescence thermally activated delayed fluorescence material was observed. As shown in Figure 5 , it can be seen that the previous part of the lifetime curve graph showed an upward trend during the change from 77 K to room temperature, which indicated that the chiral compound prepared in the present application simultaneously had the effects of thermally activated delayed fluorescence and room temperature phosphorescence.

Claims

1. A method for preparing a circularly polarized luminescent thermally activated delayed fluorescence material, characterized by: The structural formula of the circularly polarized luminescent thermally activated delayed fluorescence material is X is one of C, O and S; when X is C, Y is a -CH3 group.

2. The preparation method of the circularly polarized luminescent thermally activated delayed fluorescence material according to claim 1, characterized in that: (1) preparing compound 1 Dissolve phenothiazine in DMF, add sodium hydride, stir under nitrogen protection, then add 4, 4'-dibromodiphenyl sulfone, and react for 24-48 hours; After the reaction is completed, the temperature is lowered to room temperature, water is extracted for at least twice, the organic phase solution is collected, anhydrous sodium sulfate is added to the organic phase solution to absorb excess water, the upper clear liquid is obtained by filtration, and the organic solvent is distilled out by rotary evaporation to obtain yellow solid, which is compound 1; (2) preparing compound 2 Dissolve compound 1 in toluene, add 1-phenyl-1, 2, 3, 4-tetrahydroisoquinoline, Pd2dba3 and potassium tert-butoxide, stir under nitrogen protection, heat to 80-120 DEG C and react for 24-48 hours; After the reaction is completed, the temperature is lowered to room temperature, water is extracted for at least twice, the organic phase solution is collected, anhydrous sodium sulfate is added to the organic phase solution to absorb excess water, the upper clear liquid is obtained by filtration, and the organic solvent is distilled out by rotary evaporation to obtain yellow solid, which is compound 2.

3. The method of producing a circularly polarized luminescent thermally activated delayed fluorescence material according to claim 2, characterized by: The 1-phenyl-1, 2, 3, 4-tetrahydroisoquinoline in step (2) is R-1-phenyl-1, 2, 3, 4-tetrahydroisoquinoline, and the structural formula of the compound 2 is 4. The method of producing a circularly polarized luminescent thermally activated delayed fluorescence material according to claim 2, characterized by: The 1-phenyl-1, 2, 3, 4-tetrahydroisoquinoline in step (2) is S-1-phenyl-1, 2, 3, 4-tetrahydroisoquinoline, and the structural formula of the compound 2 is 5. The preparation method of the circularly polarized luminescent thermally activated delayed fluorescence material according to claim 1, characterized in that: (1) preparing compound 1 Dissolve acridine in DMF, add sodium hydride, stir under nitrogen protection, then add 4, 4'-dibromodiphenyl sulfone, and react for 24-48 hours; After the reaction is completed, the temperature is lowered to room temperature, water is extracted for at least twice, the organic phase solution is collected, anhydrous sodium sulfate is added to the organic phase solution to absorb excess water, the upper clear liquid is obtained by filtration, and the organic solvent is distilled out by rotary evaporation to obtain yellow solid, which is compound 1; (2) preparing compound 2 Dissolve compound 1 in toluene, add S-1-phenyl-1, 2, 3, 4-tetrahydroisoquinoline, Pd2dba3 and potassium tert-butoxide, stir under nitrogen protection, heat to 80-120 DEG C and react for 24-48 hours; After the reaction is completed, the temperature is lowered to room temperature, water is extracted for at least twice, the organic phase solution is collected, anhydrous sodium sulfate is added to the organic phase solution to absorb excess water, the upper clear liquid is obtained by filtration, and the organic solvent is distilled out by rotary evaporation to obtain yellow solid, which is compound 2.

6. The preparation method of the circularly polarized luminescent thermally activated delayed fluorescence material according to claim 1, characterized in that: (1) preparing compound 1 Dissolve acridine in DMF, add sodium hydride, stir under nitrogen protection, then add 4, 4'-dibromodiphenyl sulfone, and react for 24-48 hours; After the reaction, when the temperature drops to room temperature, extract with water at least twice, collect the organic phase solution, add anhydrous sodium sulfate to absorb excess water, filter to obtain the supernatant, rotary evaporate the organic solvent to obtain yellow solid, which is compound 1; (2) Preparation of compound 2 Compound 1 is dissolved in toluene, R-1-phenyl-1,2,3,4-tetrahydroisoquinoline, Pd2dba3, potassium tert-butoxide are added, stirred under nitrogen protection, heated to 80-120℃ for 24-48h; After the reaction, when the temperature drops to room temperature, extract with water at least twice, collect the organic phase solution, add anhydrous sodium sulfate to absorb excess water, filter to obtain the supernatant, rotary evaporate the organic solvent to obtain yellow solid, which is the target product compound 2.

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