Organic light-emitting compound as well as preparation method and application thereof

Abstract

The invention provides an organic light-emitting compound as well as a preparation method and application thereof, and belongs to the technical field of preparation of organic light-emitting materials. The organic light-emitting compound is a monomer material I, and the chemical structural formula of the monomer material I is # imgabs0 #. The luminescent property of the material can be improved.

Description

Technical Field

[0001] The present disclosure belongs to the technical field of the preparation of organic light-emitting materials, and particularly relates to an organic light-emitting compound, a preparation method thereof, and an application thereof. Background Art

[0002] In the field of luminescence, there are a wide variety of organic materials and they are widely used. Especially for BODIPY (boron dipyrromethene complexes) in boron-nitrogen organic light-emitting materials, it has attracted great attention due to its excellent optical properties, thermal stability, and chemical versatility. Although BODIPY organic light-emitting materials have strong absorption and high emission quantum yields, the small Stokes shift (~20 nm) is the main obstacle to their application. Therefore, it is of great significance to develop new materials that can replace BODIPY organic light-emitting materials. Summary of the Invention

[0003] Embodiments of the present disclosure provide an organic light-emitting compound, a preparation method thereof, and an application thereof, which can increase the Stokes shift by improving the solid electronic structure of the material, improve the luminescence performance of the material, and expand the application scope of the material. The technical solutions are as follows:

[0004] Embodiments of the present disclosure provide an organic light-emitting compound, and the organic light-emitting compound is monomer material I. The chemical structural formula of the monomer material I is:

[0005]

[0006] On the other hand, the present disclosure also provides a preparation method of an organic light-emitting compound. The preparation method prepares the organic light-emitting compound described above according to the following synthetic route: in a tetrahydrofuran solution of compound A, add compound B, Na2CO3, and tetrakis(triphenylphosphine)palladium, react under reflux, and purify and separate to obtain powdery compound C; in a tetrahydrofuran solution of the compound C, add compound D and potassium tert-butoxide, react under reflux, and purify and separate to obtain the monomer material I; wherein the chemical structural formulas of the compound A, the compound B, the compound C, and the compound D are as follows in sequence:

[0007]

[0008] In yet another implementation manner of the present disclosure, the compound A is synthesized according to the following route: 3,6-Di-tert-butylcarbazole and Cs2CO3 are mixed with ultra-dry dimethylformamide under the protection of an inert gas to obtain a suspension; the suspension is stirred and compound A1 is added, and the temperature is raised for reaction to obtain a mixture, and the mixture is purified to obtain compound A2; compound A2 and ultra-dry mesitylene are placed in a reaction vessel, and a catalytic reaction is carried out with n-butyllithium under an Ar atmosphere, boron tribromide is added below -40 °C and then the temperature is raised to room temperature for reaction, and diethylenetriamine is injected at 0 °C, the temperature is raised for reaction, and the product is quenched with ice water, and purified and separated to obtain compound A3; compound A3 is dissolved in 1,4-dioxane, bis(pinacolato)diboron, potassium acetate, and [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium are added, and after reaction refluxing overnight, it is purified and separated to obtain the compound A; wherein the chemical structural formulas of the compound A1, the compound A2, and the compound A3 are as follows in sequence:

[0009]

[0010] In yet another implementation manner of the present disclosure, the compound B is synthesized according to the following route: compound B1 is dissolved in acetonitrile, 1,4-dibromobutane and K2CO3 are added, and the mixture is refluxed for reaction, and purified and separated to obtain compound B2; compound B2, 1,4-dimethoxybenzene, and paraformaldehyde are dispersed in a 1,2-dichloroethane solution, boron trifluoride diethyl ether solution is added and stirred, and then purified and separated to obtain compound B3; K2CO3 and KI are added to the dimethylformamide solution of 3-bromo-5-hydroxybenzaldehyde, after heating and stirring, compound B3 is added for reaction, and purified and separated to obtain the compound B; wherein the chemical structural formulas of the compound B1, the compound B2, and the compound B3 are as follows in sequence:

[0011]

[0012] In yet another implementation manner of the present disclosure, the compound D is synthesized according to the following route: under an Ar atmosphere, compound D1 is dissolved in dimethyl sulfoxide, 1-bromodecane and potassium hydroxide are added, and after refluxing for reaction, it is purified and separated to obtain compound D2; compound D2 and paraformaldehyde are suspended in glacial acetic acid to form a compound J solution; 33% HBr is dissolved in the glacial acetic acid to form a mixed solution; the mixed solution is dropped into the compound J solution, after heating and stirring, it is refluxed for reaction, and purified to obtain compound D3; compound D3 and triethyl phosphite are heated and stirred, after the reaction is completed, the mixture is purified and separated to obtain the compound D; wherein the chemical structural formulas of the compound D1, the compound D2, and the compound D3 are as follows in sequence:

[0013]

[0014] In another aspect, the present disclosure also provides an application of an organic light-emitting material, where the organic light-emitting material is the organic light-emitting material described above, and the organic light-emitting material is applied to a blue light-emitting device.

[0015] In yet another aspect, the present disclosure also provides a polymer light-emitting material, where the monomer of the polymer light-emitting material is the monomer material I described above.

[0016] In yet another aspect, the present disclosure also provides a preparation method of a polymer light-emitting material, where the preparation method is used for the polymer light-emitting material described above, and the preparation method includes: self-assembling the monomer material I described above to obtain the polymer light-emitting material.

[0017] In yet another aspect, the present disclosure also provides an application of a polymer light-emitting material, where the polymer light-emitting material is the polymer light-emitting material described above, and the polymer light-emitting material is applied to a blue light-emitting device.

[0018] In yet another implementation manner of the present disclosure, the polymer light-emitting material is applied in the blue light-emitting device in a thin film structure.

[0019] The beneficial effects brought by the technical solution provided by the embodiments of the present disclosure are as follows:

[0020] The present disclosure proposes an organic light-emitting material, which is monomer material I, and its chemical structure is a supramolecular monomer (APOPV) with a vertical complementary cross-linked AABB type: outside the light-emitting structure centered on ethylene phenylene, a boron nitride compound is introduced to improve the solid electronic structure of the monomer material, and then the donor-acceptor pairs of macrocycles and chain molecules are connected, so that the monomer material I self-polymerizes to form a vertically complementary interpenetrating network structure polymer, further increasing the Stokes shift.

[0021] Moreover, the polymer has flexible and stretchable mechanical properties, expanding the application range of the organic light-emitting material. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the technical solutions in the embodiments of the present disclosure, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the following drawings are only some embodiments of the present disclosure. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0023] Figure 1 is a flowchart of a preparation method of an organic light-emitting material provided by an embodiment of the present disclosure;

[0024] Figure 2It is a flowchart of another method for preparing an organic light-emitting material provided by an embodiment of the present disclosure;

[0025] Figure 3 It is an ultraviolet absorption spectrum diagram of the organic light-emitting material provided by an embodiment of the present disclosure;

[0026] Figure 4 It is a fluorescence spectrum diagram of the organic light-emitting material provided by an embodiment of the present disclosure;

[0027] Figure 5 It is a mass spectrum diagram of the organic light-emitting material provided by an embodiment of the present disclosure. Detailed implementation manners

[0028] To make the objectives, technical solutions, and advantages of the present disclosure clearer, the following will further describe the embodiments of the present disclosure in detail with reference to the accompanying drawings.

[0029] An embodiment of the present disclosure provides an organic light-emitting compound, and the organic light-emitting compound is monomer material I. The chemical structural formula of monomer material I is:

[0030]

[0031] The present disclosure provides an organic light-emitting material, and the organic light-emitting material is monomer material I. Since a macrocyclic structure and a chain-like molecular structure are introduced into the chemical structural formula of monomer material I (it can be seen from the middle of the chemical structural formula that there is a chain-like molecule, and the chain-like molecule and the groups on the left and right sides can form a macrocyclic structure), a vertically complementary donor-acceptor pair is formed in the monomer material I, greatly improving the solid electronic structure of the monomer material, and enabling the monomer material I to have good light-emitting performance. Moreover, by means of a phosphate group, each functional group is simply and ingeniously connected, enabling the monomer material I to have the characteristic of self-assembling into an interpenetrating network polymer. When the material is used, it can self-assemble into a polymer, thus greatly improving the mechanical properties of the material.

[0032] On the other hand, an embodiment of the present disclosure also provides a method for preparing an organic light-emitting compound. The preparation method prepares the organic light-emitting compound according to the following synthetic route:

[0033]

[0034] Among them, as Figure 1 shown, the preparation method includes:

[0035] S101: In a tetrahydrofuran solution of compound A, add compound B, Na2CO3, and tetrakis(triphenylphosphine)palladium, react under reflux overnight, and purify and separate to obtain powdery compound C.

[0036] S102: In a tetrahydrofuran solution of compound C, add compound D and potassium tert-butoxide, reflux the reaction, and purify and separate to obtain monomer material I.

[0037] Among them, the chemical structural formulas of compound A, compound B, compound C, and compound D are as follows in sequence:

[0038]

[0039] The above preparation process is simple. Each functional group can be ingeniously and simply connected by means of a phosphate group, enabling monomer material I to have the property of self-assembling into an interpenetrating network polymer, and improving the mechanical properties of the material.

[0040] On the other hand, the embodiments of the present disclosure also provide another preparation method of an organic light-emitting material, as Figure 2 shown, the preparation method includes:

[0041] S201: Synthesize compound A.

[0042] Optionally, for the chemical structural formula of compound A, refer to the foregoing. Compound A is synthesized according to the following route:

[0043]

[0044] Exemplarily, S201 includes:

[0045] 2011: Mix 3,6-di-tert-butylcarbazole with Cs2CO3 in an inert gas and ultra-dry dimethylformamide (i.e., anhydrous DMF) to obtain a suspension.

[0046] Exemplarily, the inert gas can be Ar gas.

[0047] 2012: Stir the suspension and add compound A1, raise the temperature for reaction to obtain a mixture, and purify the mixture to obtain compound A2.

[0048] For example, the suspension can be stirred at 50 - 65 °C for 10 - 20 min and add compound A1, raise the temperature to 155 °C - 170 °C for reaction overnight to obtain a mixture, and purify the mixture to obtain compound A2.

[0049] The above-mentioned overnight usually means 10 h - 15 h.

[0050] 2013: Place compound A2 and ultra-dry mesitylene (i.e., anhydrous mesitylene) in a reaction vessel, carry out a catalytic reaction with n-butyllithium under an inert gas atmosphere, add boron tribromide below -35 °C and then raise the temperature to room temperature for reaction, inject diethylenetriamine at 0 °C, raise the temperature for reaction, and quench the product with ice water, and purify and separate to obtain compound A3.

[0051] In this embodiment, compound A2 and ultra-dry mesitylene (i.e., anhydrous mesitylene) can be placed in a reaction container under an Ar atmosphere, and catalyzed by n-butyl lithium for a short-time reaction at low temperature in an ice bath, and then the reaction is continued at room temperature. Boron tribromide is quickly added below -35°C, and then the reaction is carried out for a short time at low temperature. The temperature is then raised to room temperature to continue the reaction, and diethylenetriamine (DIEA) is injected at 0°C. The temperature is raised to above 180°C to react overnight, and the product is quenched with ice water, purified and separated to obtain compound A3.

[0052] The reaction vessel may be a pressure-resistant thick-walled container.

[0053] 2014: Compound A3 was dissolved in 1,4-dioxane, and diboric acid pinacol ester, potassium acetate, and [1,1-bis(diphenylphosphino)ferrocene]palladium dichloride were added. The reaction was refluxed overnight, and compound A was purified and separated.

[0054] For example, compound A can be obtained in the following manner: 3,6-di-tert-butylcarbazole (12.29 g, 44 mmol) and Cs2CO3 (32.50 g, 100 mmol) are added to a 250 mL double-mouthed round-bottomed flask in sequence, and then, under an Ar atmosphere, 50 ml of ultra-dry DMF is injected through a syringe to obtain a suspension, which is stirred at 60 ° C for 15 minutes. Finally, compound A1, 5-bromo-2-chloro-1,3-difluorobenzene (5.44 g, 20 mmol) are added from the side of the reaction bottle at one time, and the temperature is raised to 155 ° C for reaction for 12 hours. After the reaction is completed, it is cooled to room temperature, the insoluble inorganic salts are filtered out, and then the high-boiling DMF solvent is removed by vacuum concentration. The residue is purified by a column machine to obtain 13.61 g of white powder of intermediate A2 with a yield of 86%.

[0055] In this example, the obtained compound A2 was characterized by nuclear magnetic hydrogen spectrum 1H NMR (400 MHz, CDCl3), and the characteristic peaks corresponding to the characterization results were: A2, 1H NMR (400 MHz, CDCl3): δ8.08 (s, 4H), 7.68 (s, 2H), 7.45 (d, J = 8.6 Hz, 4H), 7.07 (d, J = 8.5 Hz, 4H), 1.40 (s, 36H). The above standard results are consistent with the characteristic peaks of the standard compound A2, and it can be inferred that the above compound is compound A2.

[0056] Next, add intermediate A2 (3.95 g, 5 mmol) and super-dry mesitylene (50 ml) to a 120 mL thick-walled pressure-resistant flask with a side port, and maintain an Ar atmosphere in the flask. Then, dropwise add n-butyllithium (BuLi, 2.2 ml, 5.5 mmol) under an ice bath, and keep the reaction at low temperature for 20 minutes. After that, stir at room temperature for 1 hour. Then, quickly inject boron tribromide (0.95 mL, 10 mmol) at -40 °C, keep it at low temperature for 15 minutes, and then naturally warm up to room temperature and stir for 0.5 hour. Finally, continue to inject DIEA (1.6 mL, 10 mmol) under an ice bath, seal the tube, heat up to 180 °C, and stir for 12 hours. After the reaction is completed, cool to room temperature, add 5 mL of ice water to quench the reaction mixture, then extract with 100 mL of dichloromethane, and concentrate the combined organic layers under vacuum. The residue is purified by a column chromatograph to obtain 1.94 g of a yellow powder of product A3, with a yield of 54%.

[0057] In this example, the obtained compound A3 was characterized by 1H NMR (400 MHz, CDCl3). The characteristic peaks corresponding to the characterization results were: A3, 1H NMR (400 MHz, CDCl3): δ 9.05 (s, 2H), 8.41 (s, 2H), 8.30 (s, 2H), 8.21 (d, J = 11.3 Hz, 4H), 7.64 (d, J = 8.7 Hz, 2H), 1.67 (s, 18H), 1.53 (s, 18H). The above standard results are consistent with the characteristic peaks of the standard compound A3, and it can be inferred that the above compound is compound A3.

[0058] Next, dissolve compound A3 (500 mg, 0.696 mmol) in 30 ml of 1,4-dioxane, add bis(pinacolato)diboron (441 mg, 1.74 mmol), potassium acetate (204 mg, 2.088 mmol), and [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium (51 mg, 0.0696 mmol), and reflux at 110 °C for 12 hours. After the reaction is completed, cool to room temperature, then extract with dichloromethane, and concentrate the combined organic layers under vacuum. The residue is purified by a column chromatograph to obtain 479 mg of a yellow powder of product A, with a yield of 90%.

[0059] The above method can efficiently synthesize compound A. Moreover, in this example, the obtained compound A was characterized by 1H NMR 1Characterized by \(^{1}H\) NMR (400 MHz, \(CDCl_{3}\)), the characteristic peaks corresponding to the characterization results are consistent with the standard characteristic peaks of the actual compound A. The characteristic peaks corresponding to the characterization results are: A, \(\delta 9.14\) (s, 2H), 8.79 (s, 2H), 8.54 (d, \(J = 8.7\) Hz, 2H), 8.48 (s, 2H), 8.27 (s, 2H), 7.74 (d, \(J = 8.8\) Hz, 2H), 1.68 (s, 18H), 1.55 (s, 18H), 1.50 (s, 12H). The above standard results are consistent with the characteristic peaks of the standard compound A, and it can be inferred that the above compound is compound A.

[0060] S202: Synthesize compound B.

[0061] Optionally, the chemical structural formula of compound B is shown in the previous text. Compound B is synthesized according to the following route:

[0062]

[0063] 2021: Dissolve compound B1 (p-methoxyphenol) in acetonitrile, add 1,4-dibromobutane and \(K_{2}CO_{3}\), and reflux the reaction. After purification and separation, compound B2 is obtained.

[0064] 2022: Disperse compound B2, 1,4-dimethoxybenzene, and paraformaldehyde in a 1,2-dichloroethane solution. After adding boron trifluoride diethyl etherate solution and stirring, compound B3 is obtained by purification and separation.

[0065] 2023: Add \(K_{2}CO_{3}\) and KI to the DMF solution of 3-bromo-5-hydroxybenzaldehyde. After heating and stirring, add compound B3 to react, and compound B is obtained by purification and separation.

[0066] For example, compound B can be obtained in the following way: First, dissolve p-methoxyphenol (0.62 g, 0.005 mol) (that is, compound B1) in 20 ml of acetonitrile, add 1,4-dibromobutane (6.47 g, 0.03 mol) and \(K_{2}CO_{3}\) (4.14 g, 0.03 mol). React under reflux at 90 °C for 12 hours. After the reaction is completed, cool to room temperature, and then extract with dichloromethane. The combined organic layers are concentrated in vacuo. The residue is purified by a column machine to obtain 1.03 g of the powder of product B2, and the yield is 80%.

[0067] In this example, the obtained compound B2 was characterized by 1H NMR (400 MHz, CDCl3). The characteristic peaks corresponding to the characterization results were: B2, 1H NMR (400 MHz, CDCl3): δ 6.83 (s, 4H), 3.94 (t, J = 5.9 Hz, 2H), 3.77 (s, 3H), 3.48 (dd, J = 12.2, 5.5 Hz, 2H), 2.09–2.04 (m, 2H), 1.96–1.88 (m, 2H), which were consistent with the characteristic peaks of the standard compound B2.

[0068] Then, compound B2 (0.43 g, 1.67 mmol), 1,4-dimethoxybenzene (2.76 g, 20.04 mmol) and paraformaldehyde (1 g, 33.4 mmol) were dispersed in 1,2-dichloroethane solution (250 ml). After the mixture was stirred at room temperature for 15 - 30 minutes (such as 20 minutes), 2 ml of boron trifluoride diethyl ether solution was added, and stirring was continued for 20 - 40 minutes (such as 30 minutes). After the reaction was completed, extraction was carried out with dichloromethane, and the organic layer was concentrated under vacuum. The residue was purified by a column chromatography machine to separate 290 mg of white powder of product B3, with a yield of 20%.

[0069] To the DMF solution (40 mL) of 3-bromo-5-hydroxybenzaldehyde (1.53 g, 7.65 mmol), K2CO3 (1.44 g, 10.44 mmol) and KI (0.17 g, 1.044 mmol) were added. After stirring at 80 °C for 0.5 hour, compound B3 (6.06 g, 6.96 mmol) was added for reaction and stirring was continued at 80 °C for another 10 hours. After cooling to room temperature, extraction was carried out with dichloromethane, and the organic layer was concentrated under vacuum. The residue was purified by a column chromatography machine to separate 4.82 g of white product of compound B, with a yield of 70%.

[0070] The above method can efficiently synthesize compound B. Moreover, after obtaining compound B, 1H NMR 1 H NMR (400 MHz, CDCl3) characterization was carried out. The characteristic peaks corresponding to the characterization results were: δ 11.45 (d, J = 2.1 Hz, 1H), 8.83 (t, J = 2.9 Hz, 3H), 8.38–8.28 (m, 10H), 5.57–5.51 (m, 2H), 5.48 (d, J = 6.5 Hz, 2H), 5.34 (d, J = 6.6 Hz, 10H), 5.24–5.17 (m, 27H), 3.50 (dq, J = 18.9, 7.2 Hz, 4H). The above standard results were consistent with the characteristic peaks of the standard compound B, and it could be inferred that the above compound was compound B.

[0071] S203: Synthesize compound D.

[0072] Optionally, for the chemical structural formula of Compound D, refer to the foregoing text. Compound D is synthesized according to the following route:

[0073]

[0074] 2031: Under an Ar atmosphere, dissolve Compound D1 (1,4-benzenediol) in dimethyl sulfoxide (DMSO), add 1-bromodecane and potassium hydroxide, and after refluxing overnight, purify and isolate to obtain Compound D2.

[0075] 2032: Suspend Compound D2 and paraformaldehyde in glacial acetic acid to form a solution of Compound J;

[0076] 2033: Dissolve 33% HBr in glacial acetic acid to form a mixed solution;

[0077] 2034: Drop the mixed solution into the solution of Compound J, heat and stir, and then reflux. Purify to obtain Compound D3.

[0078] 2035: Heat and stir Compound D3 and triethyl phosphite. After the reaction is completed, purify and isolate the mixture to obtain Compound D.

[0079] Exemplarily, under an Ar atmosphere, in a DMSO (30 ml) solution of 1,4-benzenediol (475 mg, 4.31 mmol), add 1-bromodecane (2 g, 9.042 mmol) and KOH (1.83 g, 32.6 mmol), reflux for 11 h. After the reaction is completed, extract with dichloromethane and concentrate the organic layer under vacuum. The residue is purified by a column chromatograph to isolate 874 mg of a white product of D2 with a yield of 52%.

[0080] In this example, the obtained Compound D2 was characterized by 1H NMR (400 MHz, CDCl3). The characteristic peaks corresponding to the characterization results were: D2, 1H NMR (400 MHz, CDCl3): δ 6.82 (s, 4H), 3.89 (t, J = 6.5 Hz, 4H), 1.81–1.69 (m, 4H), 1.56 (s, 1H), 1.43 (d, J = 7.1 Hz, 4H), 1.29 (d, J = 13.4 Hz, 24H), 0.88 (t, J = 6.2 Hz, 5H). The above standard results are consistent with the characteristic peaks of the standard Compound D2, and it can be inferred that the above compound is Compound D2.

[0081] Compound D2 (590 mg, 1.8 mmol) and paraformaldehyde (165 mg, 5.49 mmol) were suspended in glacial acetic acid (40 ml). 33% HBr (10 ml, 55 mmol) was dissolved in glacial acetic acid (20 ml), and the mixed solution was added dropwise to the solution of compound J. The mixture was stirred vigorously at 55 °C and refluxed for 22 h. After the reaction was completed, ice water was added, and a white powder was formed. Then, it was filtered by suction, washed with ice water until the solution was neutral, and the filter residue was collected and dried in vacuo to obtain 750 mg of the white product of D3 with a yield of 81%.

[0082] In this example, the obtained compound D3 was characterized by 1H NMR (400 MHz, CDCl3). The characteristic peaks corresponding to the characterization results were: D3, 1H NMR (400 MHz, CDCl3): δ 6.83 (d, J = 11.4 Hz, 2H), 4.53 (s, 4H), 3.98 (t, J = 6.3 Hz, 4H), 1.85–1.76 (m, 4H), 1.48 (dd, J = 14.0, 7.0 Hz, 5H), 1.28 (s, 24H), 0.88 (t, J = 5.4 Hz, 5H). The above standard results were consistent with the characteristic peaks of the standard compound D3, and it could be inferred that the above compound was compound D3.

[0083] Compound D3 (1.66 g, 2.89 mmol) and triethyl phosphite (1.92 g, 11.56 mmol) were placed in a 100-ml flask and stirred vigorously at 130 °C for 24 h. After the reaction was completed, it was cooled to room temperature, extracted with dichloromethane, and the organic layer was concentrated in vacuo and dried. 1.6 g of the white product of D was obtained with a yield of 80%.

[0084] The above method could efficiently synthesize compound D. Moreover, after obtaining compound D, it was characterized by 1H NMR (400 MHz, CDCl3). The characteristic peaks corresponding to the characterization results were:

[0085] D, 1H NMR (400 MHz, CDCl3): δ 6.91 (s, 2H), 3.91 (t, J = 6.3 Hz, 4H), 3.22 (d, J = 20.3 Hz, 4H), 1.72 (d, J = 12.8 Hz, 12H), 1.24 (dd, J = 14.7, 7.1 Hz, 40H), 0.88 (t, J = 6.1 Hz, 6H). According to the characteristics of the characteristic peaks, it could be inferred that the above synthesized compound was compound D. The above standard results were consistent with the characteristic peaks of the standard compound D, and it could be inferred that the above compound was compound D.

[0086] S204: Synthesize monomer material I.

[0087] Optionally, the monomeric material I is obtained according to S101 and S102 in the foregoing steps.

[0088] Exemplarily, to a solution of compound A (464 mg, 0.606 mmol) in THF (30 ml), compound B (500 mg, 0.505 mmol), Na2CO3 (1.07 g, 10 mmol), and tetrakis(triphenylphosphine)palladium (60 mg, 0.05 mmol) were added. The reaction was refluxed at 85 °C for 12 h, cooled to room temperature, and then extracted with dichloromethane. The organic layer was concentrated in vacuo. The residue was purified by column chromatography to afford 235 mg of a yellow powder of compound C with a yield of 30%.

[0089] To a solution of compound C (250 mg, 0.16 mmol) in THF (20 ml), compound D (53 mg, 0.077 mmol) and potassium tert-butoxide (35 mg, 0.308 mmol) were added. The reaction was refluxed at 85 °C for 10 h, cooled to room temperature, and extracted with dichloromethane. The organic layer was concentrated in vacuo. The residue was purified by column chromatography to afford 54 mg of a yellow powder of compound C with a yield of 20%.

[0090] Compound C was characterized by 1H NMR (400 MHz, CDCl3). The corresponding characteristic peaks in the characterization results were: C, 1H NMR (400 MHz, CDCl3): δ 10.16 (s, 1H), 9.13 (s, 2H), 8.48 (s, 4H), 8.41 (d, J = 8.5 Hz, 2H), 8.28 (s, 2H), 7.96 (s, 1H), 7.68 (d, J = 9.4 Hz, 3H), 7.54 (s, 1H), 6.73 (dd, J = 21.2, 12.3 Hz, 10H), 4.27 (s, 2H), 3.96 (s, 2H), 3.75 (t, J = 17.2 Hz, 10H), 3.64–3.56 (m, 27H), 2.14 (s, 2H), 2.04 (s, 2H), 1.68 (s, 18H), 1.53 (s, 18H). The above standard results were consistent with the characteristic peaks of the standard compound C, and it could be inferred that the above compound was compound C.

[0091] To a solution of compound C (250 mg, 0.16 mmol) in THF (20 ml), compound D (53 mg, 0.077 mmol) and potassium tert-butoxide (35 mg, 0.308 mmol) were added. The reaction was refluxed at 85 °C for 10 h, cooled to room temperature, and extracted with dichloromethane. The organic layer was concentrated in vacuo. The residue was purified by column chromatography to afford 54 mg of a yellow powder of monomeric material I with a yield of 20%.

[0092] For the monomer material I synthesized by the above method, in the embodiments of the present disclosure, it is characterized in the following aspects.

[0093] (1) Luminescence performance: The above monomer material is dissolved in toluene to form a toluene solution of the monomer material (concentration is 10 - 5 mol·L -1 ), and the toluene solution of the monomer material is placed in an ultraviolet-visible-near-infrared spectrophotometer for testing to obtain Figure 3 . From Figure 3 , it can be seen that there are three absorption peaks in the ultraviolet-visible absorption spectrum at 270 nm - 330 nm, 360 nm - 430 nm, and 440 nm - 500 nm, indicating that the material can absorb ultraviolet light and has a chromophore group to emit light.

[0094] The fluorescence emission (excited at a wavelength of 290 nm) spectrum of the toluene solution of the monomer material is as Figure 4 shown, and the maximum fluorescence emission appears at 487 nm. It can be seen that the above material has a narrow emission peak at 487 nm as a blue light material and is an applicable blue light material.

[0095] (2) NMR nuclear magnetic test: 0.5 ml of deuterated solvent is added to the nuclear magnetic tube containing the monomer material and dissolved thoroughly. At room temperature, it is tested with a Bruker spectrometer 400 MHz nuclear magnetic resonance analyzer, using the characteristic displacement of tetramethylsilane as the internal standard peak. The Figure 5 mass spectrum is obtained. Figure 5 It can be seen from

[0096] that the mass-to-charge ratio corresponding to one of the peaks is 3485.5, corresponding to monomer material I.

[0097] The monomer material in the present disclosure forms a vertically complementary donor-acceptor pair by introducing a macrocyclic structure and a chain-like molecule, improving the solid electronic structure of the material and adjusting the luminescence characteristics of the material; by means of the phosphate group, each functional group is simply and ingeniously connected, enabling the monomer to have the characteristic of self-assembling into an interpenetrating network polymer, enhancing the mechanical properties of the material and simplifying the synthesis process. The material has a narrow emission peak at 487 nm as a blue light material and is an applicable blue light material.

[0097] On the other hand, the embodiments of the present disclosure also provide a polymer light-emitting material, and the monomer of the polymer light-emitting material is the monomer material I described above.

[0098] On the other hand, the embodiments of the present disclosure also provide a preparation method of a polymer light-emitting material. The preparation method is used to prepare the polymer light-emitting material described above, and the preparation method includes: self-assembling the monomer material I to obtain the polymer light-emitting material.

[0099] Optionally, the monomer material I undergoes self-assembly in an aqueous solution.

[0100] In another aspect, the embodiments of the present disclosure also provide an application of a polymer light-emitting material. The polymer light-emitting material is the aforementioned polymer light-emitting material, and the polymer light-emitting material is applied to a blue light-emitting device.

[0101] In another aspect, the embodiments of the present disclosure also provide an application of an organic light-emitting material. The organic light-emitting material is the organic light-emitting material described above, and the organic light-emitting material is applied to a blue light-emitting device.

[0102] For example, the above polymer light-emitting material can be used as a thin film in a blue light-emitting device by adopting different processes.

[0103] The mechanical properties of the thin film material prepared from the polymer light-emitting material are tested by a nanoindentation instrument (instrument model: Bruker TI980). Among them, the mechanical properties are reflected by testing parameters such as the elastic modulus and hardness of the thin film.

[0104] The elastic modulus Er is used to represent the toughness of the material and reflect its resistance to bending and deformation. The hardness H represents the ability of the material to resist indentation.

[0105] Sample preparation process: Using a 1 cm 2 silicon wafer (single-crystalline silicon wafer, single-sided polished, (100) orientation undoped) as the substrate, successively ultrasonic clean with pure water, ethanol, acetone, and toluene, and dry with argon. Immerse the substrate in a 6% octadecylsiloxane (OTS) ethanol solution for 1 hour, and then react in ammonium hydroxide vapor for more than 14 hours. Take out the substrate, ultrasonic in toluene for 5 minutes, and dry with argon.

[0106] Prepare a toluene solution of monomer material I with a concentration of 8 mg / ml and filter it through a PVDF membrane with a pore size of 0.22 microns.

[0107] Sample 1 preparation: Quickly drop 20 microliters of the above toluene solution of monomer material I in the center of each substrate, and then anneal on a hot stage at 120 °C for 20 minutes. The performance test is completed within 48 hours after the preparation.

[0108] Sample 2 (low-speed spin-coated sample) preparation: Spin-coat the toluene solution of monomer material I on the silicon wafer at a speed of 1000 rpm for 30 seconds, and then anneal on a hot stage at 120 °C for 20 minutes. The performance test is completed within 48 hours after the preparation.

[0109] Sample 3 preparation (drop-casting film under the preparation conditions of a single molecular layer for different substrate surface modifications): Using a 1 cm 2Using a silicon wafer (single-crystalline silicon wafer, single-sided polished, (100) orientation undoped) as the substrate, it is ultrasonically cleaned successively with pure water, ethanol, acetone, and toluene, and then dried with argon. The substrate is immersed in a 1% octadecylsiloxane (OTS) ethanol solution for 1 hour, and then reacted in ammonium hydroxide vapor for more than 14 hours. The substrate is taken out, ultrasonically cleaned in toluene for 5 minutes, and dried with argon.

[0110] Prepare a toluene solution of monomer material I with a concentration of 8 mg / ml, and filter it through a PVDF membrane with a pore size of 0.22 microns. Quickly drop 20 microliters of the toluene solution of monomer material I at the center of each substrate, and then anneal it on a hot plate at 120 °C for 20 minutes. The performance test is completed within 48 hours after the preparation.

[0111] Sample 4 preparation (spin-coating sample at high speed): Spin-coat the toluene solution of monomer material I on the silicon wafer prepared in Sample 3 at a speed of 3000 rpm for 30 seconds, and then anneal it on a hot plate at 120 °C for 20 minutes. The performance test is completed within 48 hours after the preparation.

[0112] Select three detection points at different positions in each sample for performance testing. The corresponding Table 1 is obtained.

[0113] Table 1 Detection data

[0114]

[0115] In Sample 1, the elastic modulus and hardness data at different points are as follows:

[0116] Point 1: Er = 1.221750 GPa, H = 0.078636 Gpa;

[0117] Point 2: Er = 1.273135 GPa, H = 0.081534 GPa;

[0118] Point 3: Er = 1.387799 GPa, H = 0.094090 GPa.

[0119] In Sample 2, the elastic modulus and hardness data at different points are as follows:

[0120] Point 1: Er = 2.016757 GPa, H = 0.038334 GPa;

[0121] Point 2: Er = 2.008279 GPa, H = 0.046392 GPa;

[0122] Point 3: Er = 2.267327 GPa, H = 0.051759 GPa.

[0123] In Sample 3, the elastic modulus and hardness data at different points are as follows:

[0124] Point 1: Er = 3.121125 GPa, H = 0.102377 GPa;

[0125] Point 2: Er = 6.490819 GPa, H = 0.383067 GPa;

[0126] Point 3: Er = 3.712317 GPa, H = 0.145998 GPa.

[0127] In sample 4, the elastic modulus and hardness data at different points are as follows:

[0128] Point 1: Er = 24.388586 GPa, H = 0.272881 GPa;

[0129] Point 2: Er = 20.756484 GPa, H = 0.260058 GPa;

[0130] Point 3: Er = 28.210763 GPa, H = 0.266986 GPa.

[0131] Since the indentation depth is related to the film thickness and the film preparation process, for the spin-coated film (whose film thickness is usually 50 - 100), it is difficult to meet the test requirement of "indentation depth less than 10% of the film thickness", so its test results should not be accurate enough, and the data of sample 4 is abnormally high.

[0132] The preparation process of the above samples can be repeated, that is, it can be dissolved and formed into a film again. Through the flexibility performance test of the above samples, it can be seen that the monomer material has self-assembled into an elastomer (the monomer material self-assembles into a polymer light-emitting material), showing clear polymer toughness. Its solubility and mechanical properties are both good. It can be considered that the monomer material is very easy to self-assemble into a powdery polymer after the single-molecule synthesis is completed, and can be dissolved again to prepare a polymer film. At the same time, due to the self-induced assembly characteristics of the monomer material, its film layer has uniform orderliness, and its strength and toughness can meet the toughness performance requirements of flexible polymers, and its elastic modulus reaches the GPa level. In addition, since the test film layer is a nanoscale film, it can be speculated that the monomer material has broad potential in the application of thin-film devices.

[0133] The above are only optional embodiments of the present disclosure, and are not intended to limit the present disclosure. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present disclosure shall be included in the protection scope of the present disclosure.

Claims

1. An organic light-emitting compound, characterized in that, The organic light-emitting compound is monomer material I, and the chemical structural formula of the monomer material I is as follows:

2. A method for preparing an organic light-emitting compound, characterized in that, The preparation method prepares the organic light-emitting compound according to claim 1 according to the following synthetic route: In the tetrahydrofuran solution of compound A, compound B, Na2CO3 and tetrakis(triphenylphosphine)palladium are added, and the reaction is refluxed, and compound C in powder form is obtained by purification and separation; In the tetrahydrofuran solution of the compound C, compound D and potassium tert-butoxide are added, and the reaction is refluxed, and the monomer material I is obtained by purification and separation; Among them, the chemical structural formulas of the compound A, the compound B, the compound C and the compound D are as follows in sequence:

3. The preparation method according to claim 2, characterized in that, The compound A is synthesized according to the following route: 3,6-Di-tert-butylcarbazole and Cs2CO3 are mixed with ultra-dry dimethylformamide under the protection of an inert gas to obtain a suspension; The suspension is stirred and compound A1 is added, and the temperature is raised for reaction to obtain a mixture, and the mixture is purified to obtain compound A2; The compound A2 and ultra-dry mesitylene are placed in a reaction vessel, and the catalytic reaction is carried out by n-butyllithium under an inert gas atmosphere, boron tribromide is added below -35 °C and then the temperature is raised to room temperature for reaction, and diethylenetriamine is injected at 0 °C, the temperature is raised for reaction, and the product is quenched with ice water, and compound A3 is obtained by purification and separation; The compound A3 is dissolved in 1,4-dioxane, bis(pinacolato)diboron, potassium acetate, and [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium are added, and the reaction is refluxed overnight and then purified and separated to obtain the compound A; Among them, the chemical structural formulas of the compound A1, the compound A2 and the compound A3 are as follows in sequence:

4. The preparation method according to claim 2, characterized in that, The compound B is synthesized according to the following route: Compound B1 is dissolved in acetonitrile, 1,4-dibromobutane and K2CO3 are added, and the reaction is refluxed, and compound B2 is obtained by purification and separation; The compound B2, 1,4-dimethoxybenzene and paraformaldehyde are dispersed in a 1,2-dichloroethane solution, boron trifluoride diethyl ether solution is added and stirred, and then compound B3 is obtained by purification and separation; K2CO3 and KI are added to the dimethylformamide solution of 3-bromo-5-hydroxybenzaldehyde, and after heating and stirring, compound B3 is added for reaction, and the compound B is obtained by purification and separation; Among them, the chemical structural formulas of the compound B1, the compound B2 and the compound B3 are as follows in sequence:

5. The preparation method according to claim 2, wherein, The compound D is synthesized according to the following route: Under an Ar atmosphere, compound D1 is dissolved in dimethyl sulfoxide, 1-bromodecane and potassium hydroxide are added, and the reaction is refluxed, and compound D2 is obtained by purification and separation; The compound D2 and paraformaldehyde are suspended in glacial acetic acid to form a compound J solution; 33% HBr is dissolved in the glacial acetic acid to form a mixed solution; The mixed solution is added dropwise to the compound J solution, and after heating and stirring, the reaction is refluxed, and compound D3 is purified; The compound D3 and triethyl phosphite are heated and stirred, and after the reaction is completed, the mixture is purified and separated to obtain the compound D; Among them, the chemical structural formulas of the compound D1, the compound D2 and the compound D3 are as follows in sequence:

6. Application of an organic light-emitting material, characterized in that, The organic light-emitting material is the organic light-emitting material described in Claim 1, and the organic light-emitting material is applied to a blue light-emitting device.

7. A polymer light-emitting material, characterized in that, The monomer of the polymer light-emitting material is the monomer material I described in Claim 1.

8. A preparation method of a polymer light-emitting material, characterized in that, The preparation method is used to prepare the polymer light-emitting material described in Claim 7, and the preparation method includes: self-assembling the monomer material I described in Claim 1 to obtain the polymer light-emitting material.

9. Application of a polymer light-emitting material, characterized in that, The polymer light-emitting material is the polymer light-emitting material described in Claim 7, and the polymer light-emitting material is applied to a blue light-emitting device.

10. The application according to claim 9, wherein The polymer light-emitting material is applied in the blue light-emitting device in a thin film structure.

Images