A blue light-emitting material containing anthracene and dibenzofuran, a preparation method thereof, and application thereof in an organic electroluminescent device

Abstract

The present invention provides a blue light-emitting material containing anthracene and dibenzofuran, a preparation method thereof, and an application thereof in an organic electroluminescent device, belonging to the technical field of organic optoelectronic materials. The blue light-emitting material containing anthracene and dibenzofuran provided by the present invention has a structure shown in Formula I. The present invention introduces anthracene and dibenzofuran into the compound and connects the dibenzo pentacyclic compound via a carbon-carbon double bond, thereby enhancing the material's carrier transport properties. The blue light-emitting material provided by the present invention has good thermal stability, high luminous efficiency, high luminous purity, and good film-forming properties. Organic electroluminescent devices made using this blue light-emitting material can reduce operating voltage, improve luminous efficiency, enhance color purity, and extend device life.

Description

Technical Field

[0001] The present invention relates to the technical field of organic photoelectric materials, and in particular to a blue light material containing anthracene and dibenzofuran, a preparation method thereof, and application of the blue light material in organic electroluminescent devices. Background Art

[0002] Organic Light-Emitting Diodes (OLEDs) are the latest generation of display technology. They feature a multilayered, sandwich-like structure, with different film-like functional layers sandwiched between positive and negative electrode layers. Each layer has distinct functions, ensuring the proper illumination of the entire device. Compared to previous-generation liquid crystal display technology, OLEDs offer numerous advantages, including self-luminescence, wide viewing angles, fast response times, high contrast, thinness, light weight, and bendability. As a result, they are rapidly replacing the existing LCD market, particularly in high-end displays such as smartphones, computers, and televisions. OLEDs are also widely used in lighting.

[0003] OLEDs emit light by applying an electric field between the cathode and anode. Electrons and holes are injected from the electron / hole injection layer, transported through the electron / hole transport layer, and finally recombine in the light-emitting layer to produce excitons. The excitons then excite the luminescent material in the light-emitting layer, producing fluorescence or phosphorescence. Electron / hole blocking layers are sometimes used to confine charge carriers within the light-emitting layer.

[0004] In OLEDs, blue-emitting materials can not only serve as the blue light source in the three primary colors, but can also be used as the host material for green and red light through a host-guest doping system. Currently, the efficiency and lifespan of green and red phosphorescent materials have reached the requirements for commercial applications. However, due to the inherent high energy gap, the stability and optical purity of blue phosphorescent materials are poor, which cannot meet the needs of practical applications. Summary of the Invention

[0005] In view of this, the present invention aims to provide a blue light-emitting material containing anthracene and dibenzofuran, a preparation method thereof, and an application thereof in an organic electroluminescent device. The blue light-emitting material containing anthracene and dibenzofuran provided by the present invention has good thermal stability, luminous efficiency, and luminous purity.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a blue light material containing anthracene and dibenzofuran, having a structure shown in Formula I:

[0008]

[0009] In formula I, Ar is one of C1-C10 substituted or unsubstituted alkyl, C6-C30 substituted or unsubstituted aryl, and C3-C30 substituted or unsubstituted heteroaryl;

[0010] L is a single bond, a C6-C30 substituted or unsubstituted aryl group, or a C3-C30 substituted or unsubstituted heteroaryl group;

[0011] A is an oxygen atom, a sulfur atom,

[0012] Preferably, when Ar is a C1-C10 substituted or unsubstituted alkyl group, the C1-C10 substituted or unsubstituted alkyl group is a methyl group, an ethyl group, a propyl group, a hexyl group or a cyclohexyl group;

[0013] When Ar is a C6-C30 substituted or unsubstituted aryl group, the aryl group is phenyl, tolyl, biphenyl, naphthyl, phenanthryl, anthracenyl, peryl, fluoranthenyl, pyrenyl, phenylnaphthyl, naphthylphenyl, diphenylphenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9,9-spirobifluorenyl or triphenylenyl; the substituent of the aryl group is a C1-C12 alkyl group;

[0014] When Ar is a C3-C30 substituted or unsubstituted heteroaryl group, the aromatic hetero group is a benzofuranyl group, a benzothiophenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a spiro[fluorene-9,9'-xanthene], a pyridyl group, a benzonitrile phenyl group, a pyridylphenyl group, an indolyl group, a carbazole indolyl group, a fluorene carbazole group, an imidazolyl group, an oxazolyl group, a thiazolyl group, a thiadiazolyl group, a quinolyl group, an isoquinolyl group, a quinazolinyl group, a quinoxalinyl group, an azadibenzofuranyl group or an azadibenzothiophenyl group; and the substituent of the heteroaryl group is a C1-C12 alkyl group.

[0015] Preferably, L is a single bond, phenyl, naphthyl, biphenyl, anthracenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9,9-spirobifluorenyl, benzofuranyl, dibenzothiophenyl or pyridyl.

[0016] The present invention provides a method for preparing the above-mentioned blue light material containing anthracene and dibenzofuran, comprising the following steps:

[0017] A compound having a structure represented by formula a is subjected to a Heck coupling reaction with a compound having a structure represented by formula b to obtain a compound having a structure represented by formula c;

[0018]

[0019] A compound having a structure represented by formula c is subjected to a Miyaura borylation reaction with pinacol diboron to obtain a compound having a structure represented by formula d;

[0020]

[0021] A compound having a structure represented by formula e is subjected to a coupling reaction with a compound having a structure represented by formula f to obtain a compound having a structure represented by formula g;

[0022]

[0023] The compound having the structure shown in formula g is subjected to bromination reaction with Br2 to obtain a compound having the structure shown in formula h:

[0024]

[0025] The compound having the structure shown in formula d is reacted with the compound having the structure shown in formula h through a Suzuki coupling reaction to obtain a compound having the structure shown in formula I.

[0026] Preferably, the Heck coupling reaction is carried out in the presence of a base reagent and a catalyst, wherein the catalyst comprises palladium acetate;

[0027] The temperature of the Heck coupling reaction is 100-120° C., and the time is 5-8 hours.

[0028] Preferably, the Miyaura borylation reaction is carried out under the conditions of an alkaline reagent and a catalyst, and the catalyst includes palladium acetate;

[0029] The temperature of the Miyaura boronation reaction is 100-120° C., and the time is 5-8 hours.

[0030] Preferably, the coupling reaction is carried out in the presence of an alkaline reagent and a catalyst, wherein the catalyst comprises palladium acetate;

[0031] The coupling reaction temperature is 70-80°C and the time is 3-5h;

[0032] The temperature of the bromination reaction is room temperature, and the time is 5 to 8 hours.

[0033] Preferably, the Suzuki coupling reaction is carried out in the presence of an alkaline reagent and a catalyst, wherein the catalyst comprises palladium acetate;

[0034] The temperature of the Suzuki coupling reaction is 70-80° C., and the reaction time is 5-8 hours.

[0035] The present invention provides application of the above-mentioned blue light material containing anthracene and dibenzofuran in an organic electroluminescent device.

[0036] The present invention provides an organic electroluminescent device comprising an anode, a cathode and an organic layer, wherein the organic layer comprises one or more of a light-emitting layer, a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer or an electron transport layer;

[0037] At least one layer of the organic layers contains the above-mentioned blue light material containing anthracene and dibenzofuran.

[0038] The present invention provides a blue light-emitting material containing anthracene and dibenzofuran, having the structure shown in Formula I. The present invention introduces anthracene and dibenzofuran into the compound and connects the dibenzo pentacyclic compound via a carbon-carbon double bond, thereby enhancing the material's carrier transport properties. The blue light-emitting material provided by the present invention contains dibenzofuran and anthracene groups with excellent thermal stability, resulting in good thermal stability. Anthracene has a high fluorescence quantum yield, and materials containing anthracene generally have high luminous efficiency. Due to the large dihedral angle between anthracene and dibenzofuran, and the large torsion angle with the group at the other end of the carbon-carbon double bond, the degree of conjugation of the entire molecule is very limited, resulting in high luminescent purity. Furthermore, the molecular planarity is very poor, resulting in the material's excellent ability to form amorphous films. Organic electroluminescent devices fabricated using this blue light-emitting material can reduce operating voltage, increase luminous efficiency, enhance color purity, and prolong device life.

[0039] The present invention provides an organic electroluminescent device comprising an anode, a cathode, and an organic layer, characterized in that the organic layer comprises one or more of a light-emitting layer, a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer, or an electron transport layer; and at least one of the organic layers comprises the aforementioned blue light-emitting material containing anthracene and dibenzofuran. Compared to existing organic electroluminescent compounds BH-1 and BH-2, the organic electroluminescent device provided by the present invention has a lower operating voltage and a certain degree of improvement in external quantum efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 This is a schematic structural diagram of the organic electroluminescent device provided by the present invention. DETAILED DESCRIPTION

[0041] The present invention provides a blue light material containing anthracene and dibenzofuran, having a structure shown in Formula I:

[0042]

[0043] In formula I, Ar is one of C1-C10 substituted or unsubstituted alkyl, C6-C30 substituted or unsubstituted aryl, and C3-C30 substituted or unsubstituted heteroaryl;

[0044] L is a single bond, a C6-C30 substituted or unsubstituted aryl group, or a C3-C30 substituted or unsubstituted heteroaryl group;

[0045] A is an oxygen atom, a sulfur atom,

[0046] In the present invention, when Ar is a C1-C10 substituted or unsubstituted alkyl group, the C1-C10 substituted or unsubstituted alkyl group is preferably a methyl group, an ethyl group, a propyl group, a hexyl group or a cyclohexyl group;

[0047] When Ar is a C6-C30 substituted or unsubstituted aryl group, the aryl group is preferably phenyl, tolyl, biphenyl, naphthyl, phenanthryl, anthracenyl, peryl, fluoranthenyl, pyrenyl, phenylnaphthyl, naphthylphenyl, diphenylphenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9,9-spirobifluorenyl or triphenylenyl; the aryl group may be further substituted by a C1-C12 alkyl group.

[0048] When Ar is a C3-C30 substituted or unsubstituted heteroaryl group, the aromatic hetero group is a benzofuranyl group, a benzothiophenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a spiro[fluorene-9,9'-xanthene], a pyridyl group, a benzonitrile phenyl group, a pyridylphenyl group, an indolyl group, a carbazole indolyl group, a fluorene carbazole group, an imidazolyl group, an oxazolyl group, a thiazolyl group, a thiadiazolyl group, a quinolyl group, an isoquinolyl group, a quinazolinyl group, a quinoxalinyl group, an azadibenzofuranyl group or an azadibenzothiophenyl group; the oxazolyl group may be further substituted by a C1-C12 alkyl group.

[0049] In the present invention, L is preferably a single bond, phenyl, naphthyl, biphenyl, anthracenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9,9-spirobifluorenyl, benzofuranyl, dibenzothienyl or pyridyl.

[0050] As a specific embodiment of the present invention, the blue light material containing anthracene and dibenzofuran preferably has the structure shown in Table 1.

[0051] Table 1 Preferred structures of blue light materials containing anthracene and dibenzofuran

[0052]

[0053]

[0054]

[0055]

[0056] The present invention provides a method for preparing the above-mentioned blue light material containing anthracene and dibenzofuran, comprising the following steps:

[0057] A compound having a structure represented by formula a is subjected to a Heck coupling reaction with a compound having a structure represented by formula b to obtain a compound having a structure represented by formula c;

[0058]

[0059] A compound having a structure shown in formula c is subjected to a Miyaura borylation reaction with pinacol diboron to obtain a compound having a structure shown in formula d;

[0060]

[0061] A compound having a structure represented by formula e is subjected to a coupling reaction with a compound having a structure represented by formula f to obtain a compound having a structure represented by formula g;

[0062]

[0063] The compound having the structure shown in formula g is subjected to bromination reaction with Br2 to obtain a compound having the structure shown in formula h;

[0064]

[0065] The compound having the structure shown in formula d is subjected to a Suzuki coupling reaction with the compound having the structure shown in formula h to obtain a compound having the structure shown in formula I.

[0066] In the present invention, a compound having a structure represented by formula a and a compound having a structure represented by formula b undergo a Heck coupling reaction to obtain a compound having a structure represented by formula c. In the present invention, the Heck coupling reaction is preferably carried out in the presence of an alkaline reagent and a catalyst, wherein the alkaline reagent preferably includes potassium carbonate and the catalyst preferably includes palladium acetate.

[0067] In the present invention, the mass ratio of the compound having the structure represented by formula b to the compound having the structure represented by formula a is preferably 2:1.1 to 1.3, more preferably 2:1.2; the mass ratio of the compound having the structure represented by formula b to the alkaline reagent is preferably 2:1.4 to 1.6, more preferably 2:1.5, and the mass ratio of the compound having the structure represented by formula b to the catalyst is preferably 2:0.02 to 0.05, more preferably 2:0.03 to 0.04.

[0068] In the present invention, the reaction solvent used in the Heck coupling reaction is preferably DMF.

[0069] In the present invention, the temperature of the Heck coupling reaction is preferably 100-120°C, more preferably 110°C; the time is preferably 5-8 hours, more preferably 6-7 hours. In the present invention, the Heck coupling reaction is preferably carried out under nitrogen protection.

[0070] After the Heck coupling reaction, the present invention preferably performs post-treatment on the obtained Heck coupling reaction product; in the present invention, the post-treatment preferably includes the following steps:

[0071] The solvent of the Heck coupling reaction product was removed, and the resulting crude product was separated by column chromatography.

[0072] In the present invention, the method of removing the solvent is preferably concentration to dryness.

[0073] In the present invention, a compound having a structure represented by formula c undergoes a Miyaura borylation reaction with pinacol diboron to obtain a compound having a structure represented by formula d. In the present invention, the Miyaura borylation reaction is preferably carried out in the presence of an alkaline reagent and a catalyst, wherein the alkaline reagent preferably includes potassium acetate and the catalyst preferably includes palladium acetate.

[0074] In the present invention, the mass ratio of the compound having the structure represented by formula c to pinacol diboron is preferably 1.5:1.2~1.5, more preferably 1.5:1.3~1.4; the mass ratio of the compound having the structure represented by formula c to the alkaline reagent is preferably 1.5:1.2~1.5, more preferably 1.5:1.3~1.4; the mass ratio of the compound having the structure represented by formula c to the catalyst is preferably 1.5:0.02~0.05, more preferably 1.5:0.03~0.04.

[0075] In the present invention, the reaction solvent used in the Miyaura boronation reaction is preferably anhydrous toluene.

[0076] In the present invention, the temperature of the Miyaura borylation reaction is preferably 100-120°C, more preferably 110°C, and the time is preferably 5-8 hours, more preferably 6-7 hours. In the present invention, the Miyaura borylation reaction is preferably carried out under nitrogen protection.

[0077] After the Miyaura borylation reaction, the present invention preferably performs post-treatment on the obtained Miyaura borylation reaction product; in the present invention, the post-treatment preferably comprises the following steps:

[0078] The Miyaura borylation reaction product is subjected to solid-liquid separation, the organic solvent is removed, and the resulting crude product is subjected to column chromatography separation.

[0079] In the present invention, the solid-liquid separation method is preferably filtration; and the solvent removal method is preferably concentration to dryness.

[0080] In the present invention, a compound having a structure represented by formula e is subjected to a coupling reaction with a compound having a structure represented by formula f to obtain a compound having a structure represented by formula g. In the present invention, the coupling reaction is preferably carried out in the presence of an alkaline reagent and a catalyst, wherein the alkaline reagent preferably includes potassium carbonate and the catalyst preferably includes palladium acetate.

[0081] In the present invention, the mass ratio of the compound having the structure represented by formula e to the compound having the structure represented by formula f is preferably 10:6-7; the mass ratio of the compound having the structure represented by formula e to the alkaline reagent is preferably 10:6-6.5, and the mass ratio of the compound having the structure represented by formula e to the catalyst is preferably 10:0.2-0.5, more preferably 10:0.3-0.4.

[0082] In the present invention, the solvent used in the coupling reaction is preferably toluene, ethanol and water; the volume ratio of toluene, ethanol and water is preferably 2:1:1.

[0083] In the present invention, the coupling reaction temperature is preferably 70-80°C, the time is preferably 5-8 hours, more preferably 6-7 hours. In the present invention, the coupling reaction is preferably carried out under nitrogen protection.

[0084] After the coupling reaction, the present invention preferably performs post-treatment on the obtained coupling reaction product; in the present invention, the post-treatment preferably includes the following steps:

[0085] The coupling reaction product is separated, and the obtained organic phase is separated by column chromatography.

[0086] In the present invention, the compound having the structure shown in formula g is subjected to a bromination reaction with Br2 to obtain a compound having the structure shown in formula h. In the present invention, the mass ratio of the compound having the structure shown in formula g to Br2 is preferably 9:3.3 to 3.5, more preferably 9:3.4.

[0087] In the present invention, the solvent used in the bromination reaction is preferably dichloromethane.

[0088] In the present invention, the temperature of the bromination reaction is preferably room temperature, and the time is preferably 5 to 8 hours, more preferably 6 to 7 hours.

[0089] After the bromination reaction, the present invention preferably performs post-treatment on the obtained brominated product; in the present invention, the post-treatment preferably comprises the following steps:

[0090] A sodium hydroxide / sodium sulfite aqueous solution was added to the obtained brominated product to quench the reaction until neutral, the layers were separated, and the organic phase was concentrated to dryness and recrystallized.

[0091] In the present invention, the solvents used in the recrystallization are preferably toluene and ethanol.

[0092] In the present invention, a compound having a structure represented by formula d is subjected to a Suzuki coupling reaction with a compound having a structure represented by formula h to obtain a compound having a structure represented by formula I. In the present invention, the Suzuki coupling reaction is preferably carried out under the conditions of an alkaline reagent and a catalyst, the alkaline reagent preferably includes potassium carbonate, and the catalyst preferably includes palladium acetate. In the present invention, the mass ratio of the compound having a structure represented by formula h to the compound having a structure represented by formula d is preferably 1:0.85-0.90; the mass ratio of the compound having a structure represented by formula h to the alkaline reagent is preferably 1:0.35-0.45, more preferably 1:0.4, and the mass ratio of the compound having a structure represented by formula h to the catalyst is preferably 1:0.02-0.05, more preferably 1:0.03-0.04.

[0093] In the present invention, the solvent used in the Suzuki coupling reaction is preferably toluene, ethanol and water; the volume ratio of toluene, ethanol and water is preferably 2:1:1.

[0094] In the present invention, the temperature of the Suzuki coupling reaction is preferably 70-80°C, the time is preferably 5-8 hours, more preferably 6-7 hours. In the present invention, the Suzuki coupling reaction is preferably carried out under nitrogen protection.

[0095] After the Suzuki coupling reaction, the present invention preferably performs post-treatment on the obtained Suzuki coupling reaction; the post-treatment preferably comprises the following steps:

[0096] The Suzuki coupling reaction product is separated, and the obtained organic phase is separated by column chromatography.

[0097] The present invention provides the use of the above-mentioned blue-light-emitting material containing anthracene and dibenzofuran in an organic electroluminescent device. In the present invention, the organic electroluminescent device preferably includes one or more of an organic solar cell, an organic thin-film transistor, an organic photodetector, an organic field-effect transistor, an organic integrated circuit, and an organic photoreceptor.

[0098] The present invention provides an organic electroluminescent device comprising an anode, a cathode and an organic layer, wherein the organic layer comprises one or more of a light-emitting layer, a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer or an electron transport layer; and at least one of the organic layers contains the above-mentioned blue light-emitting material containing anthracene and dibenzofuran.

[0099] Preferably, the light-emitting layer in the organic layer contains the above-mentioned organic electronic material.

[0100] Preferably, the hole blocking layer in the organic layer contains the above-mentioned organic electronic material.

[0101] In the present invention, the total thickness of the organic layer is preferably 1 to 1000 nm; more preferably, the total thickness of the organic layer is 50 to 500 nm.

[0102] The organic electroluminescent device provided by the present invention can be used in combination with other materials, such as a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a blocking layer, to obtain blue light, green light, yellow light, red light, or white light when using the compound having structural formula I of the present invention.

[0103] The present invention has no special requirements on the specific materials and thicknesses of the anode, cathode and organic layer, wherein the organic layer includes a light-emitting layer, a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer or an electron transport layer, and materials and thicknesses familiar to those skilled in the art can be used.

[0104] Each organic layer in the organic electroluminescent device provided by the present invention is preferably prepared by vacuum evaporation, molecular beam evaporation, solvent dip coating, spin coating, rod coating, or inkjet printing. The metal electrode is preferably prepared by evaporation or sputtering.

[0105] The blue light-emitting material containing anthracene and dibenzofuran, its preparation method and application in organic electroluminescent devices provided by the present invention are described in detail below with reference to the examples. However, these examples should not be construed as limiting the scope of protection of the present invention.

[0106] Example 1 Synthesis of Compound 1

[0107]

[0108] (1) Synthesis of intermediate 1-1

[0109] 2-Bromo-9,9-dimethylfluorene (2.0 g, 7.32 mmol), p-chlorostyrene (1.2 g, 8.66 mmol) and potassium carbonate (1.5 g, 10.85 mmol) were added to a three-necked flask, followed by DMF (20 mL) and palladium acetate (0.04 g, 0.18 mmol). Under nitrogen protection, the reaction was stirred at 120°C for 5 h. The solvent was concentrated to dryness and the crude product was separated by column chromatography to obtain 1.8 g of an off-white solid with a yield of 75%. 1 HNMR (400MHz, CDCl3): 7.69-7.73 (m, 2H), 7.31-7.50 (m, 8H), 7.26 (d, J = 2.0Hz, 1H), 7.01-7.11 (m, 2H), 1.54 (s, 6H).

[0110] (2) Synthesis of intermediate 1-2

[0111] Intermediate 1-1 (1.5 g, 4.53 mmol), pinacol diboron (1.38 g, 5.43 mmol) and potassium acetate (1.33 g, 13.55 mmol) were added to a three-necked flask, followed by anhydrous toluene (15 mL) and palladium acetate (0.03 g, 0.13 mmol). The mixture was stirred at reflux under nitrogen for 5 h, filtered, and the solvent was concentrated to dryness. The crude product was separated by column chromatography to obtain 1.65 g of an off-white solid with a yield of 86%. 1 HNMR(400MHz, CDCl3)δ:7.69-7.73(m,4H),7.30-7.49(m,7H),7.00-7.10(m,2H),1.53(s,6H),1.24(s,12H).

[0112] (3) Synthesis of intermediate 1-3

[0113] 9-Phenyl-10-bromoanthracene (10.0 g, 30.28 mmol), dibenzofuran-2-boric acid (6.74 g, 31.79 mmol) and potassium carbonate (6.28 g, 45.44 mmol) were added to a three-necked flask, followed by toluene (60 mL), ethanol (30 mL) and deionized water (30 mL). Pd(OAc)2 (0.2 g, 0.84 mmol) and X-phos (0.4 g, 0.89 mmol) were added under nitrogen protection. After reflux for 3 h, the mixture was cooled, separated, and the organic phase was separated by column chromatography to obtain 9.7 g of a light yellow-green solid with a yield of 77%. 1 HNMR(400MHz, CDCl3):8.14-8.23(m,4H),7.97-8.02(m,2H),7.61-7.63(m,1H),7.53-7.56(m,1H),7.43-7.51(m,8H),7.32-7.41(m,4H).

[0114] (4) Synthesis of Intermediates 1-4

[0115] Intermediate 1-3 (9.0 g, 21.40 mmol) and dichloromethane (90 mL) were added to a single-necked flask, and liquid bromine (3.42 g, 21.40 mmol) was added dropwise under ice bath. The temperature was raised to room temperature and stirred for 5 h. The reaction was quenched by adding sodium hydroxide / sodium sulfite aqueous solution until neutral. The layers were separated, and the organic phase was concentrated to dryness and recrystallized from toluene and ethanol to obtain 7.8 g of a light yellow-green solid with a yield of 72%. 1HNMR (400MHz, CDCl3): 8.16-8.21(m,4H),8.07(d,J=1.2Hz,1H),8.02(d,J=1.2Hz,1H),7.61-7.65(m,2H),7.41-7.49(m,8H),7.35-7.38(m,3H).

[0116] (5) Synthesis of Compound 1

[0117] Intermediate 1-4 (1.0 g, 2.00 mmol), intermediate 1-2 (0.89 g, 2.11 mmol) and potassium carbonate (0.42 g, 3.04 mmol) were added to a three-necked flask, followed by toluene (60 mL), ethanol (30 mL) and deionized water (30 mL). Pd(OAc)2 (0.02 g, 0.084 mmol) and X-phos (0.04 g, 0.089 mmol) were added under nitrogen protection. After reflux for 5 hours, the mixture was cooled, separated, and the organic phase was separated by column chromatography to obtain 0.98 g of a light yellow-green solid with a yield of 68%. 1 H NMR(400MHz, CDCl3):8.14-8.18(m,4H),8.02(d,J=1.6Hz,1H),7.94(d,J=1.6Hz,1H),7.71-7.73(m ,1H),7.58-7.67(m,5H),7.28-7.51(m,18H),7.01-7.12(m,2H),1.55(s,6H).HRMS(ESI,m / z):[M+H] + calcd for:C 55 H 39 O,715.2995,found,715.2998.Anal.:calcd:C,92.40;H,5.36;O,2.24;found:C,92.49;H,5.28;O,2.28.

[0118] Example 2 Synthesis of Compound 6

[0119]

[0120] (1) Synthesis of Intermediate 6-1

[0121] The synthesis method refers to intermediate 1-1. 1 H NMR (400MHz, CDCl3): 8.03-8.06(m,1H),7.90(d,J=1.6Hz,1H),7.57-7.60(m,1H),7.33-7.53(m,8H),7.09(dd,J=12.8,21.6Hz,2H).

[0122] (2) Synthesis of Intermediate 6-2

[0123] The synthesis method refers to intermediate 1-2. 1 H NMR(400MHz, CDCl3):7.98-8.01(m,1H),7.87-7.89(m,1H),7.69-7.72(m,2H),7.57-7.59(m ,1H),7.37-7.51(m,5H),7.29(d,J=5.6Hz,1H),7.09(dd,J=13.2,16.4Hz,2H),1.24(s,12H).

[0124] (3) Synthesis of Compound 6

[0125] The synthesis method refers to compound 1. 1 H NMR (400MHz, CDCl3): 8.14-8.18(m,4H),8.07-8.10(m,1H),8.01-8.03(m,1H),7.94(d,J=1.6Hz,1H),7.79(d,J=1.6Hz, 1H),7.58-7.64(m,5H),7.29-7.55(m,16H),7.26(d,J=6.0Hz,1H),7.09(dd,J=12.8,16.8Hz,2H).HRMS(ESI,m / z):[M+H] + calcd for:C 52 H 33 O2,689.2475,found,689.2471.Anal.:calcd:C,90.67;H,4.68;O,4.65;found:C,90.58;H,4.75;O,4.61.

[0126] Example 3 Synthesis of Compound 11

[0127]

[0128] (1) Synthesis of Intermediate 11-1

[0129] The synthesis method refers to intermediate 1-1. 1 H NMR(400MHz, CDCl3):8.04-8.08(m,1H),7.88-7.91(m,1H),7.75-7.78(m,1H) ,7.47-7.50(m,3H),7.35-7.42(m,5H),7.28-7.32(m,1H),7.13-7.18(m,1H).

[0130] (2) Synthesis of Intermediate 11-2

[0131] The synthesis method refers to intermediate 1-2. 1 H NMR(400MHz, CDCl3):8.06-8.10(m,1H),7.88-7.91(m,1H),7.80-7.82(m,1H),7.69-7.73(m,2 H),7.44-7.48(m,2H),7.34-7.43(m,2H),7.26-7.31(m,1H),7.12-7.16(m,1H),1.24(s,12H).

[0132] (3) Synthesis of compound 11

[0133] The synthesis method refers to compound 1. 1 H NMR(400MHz, CDCl3):8.14-8.18(m,4H),8.04-8.06(m,2H),7.93-7.95(m,1H),7.86-7.88(m,1H),7.71-7.74(m,1H),7 .58-7.62(m,4H),7.51-7.55(m,2H),7.34-7.46(m,14H),7.26-7.33(m,2H),7.13-7.18(m,1H).HRMS(ESI,m / z):[M+H] + calcd for:C 52 H 33 OS,705.2247,found,705.2245.Anal.:calcd:C,88.61;H,4.58;O,2.27;S,4.55;found:C,88.73;H,4.52;O,2.23;S,4.50.

[0134] Example 4 Synthesis of Compound 13

[0135]

[0136] (1) Synthesis of Intermediate 13-1

[0137] The synthesis method refers to intermediate 1-1. 1 H NMR(400MHz, CDCl3):7.71-7.73(m,1H),7.64-7.68(m,1H),7.60(t,J=1.6Hz,1H),7.45-7.51 (m,2H),7.31-7.42(m,5H),7.26(d,J=1.6Hz,1H),7.11(dd,J=13.2,20.8Hz,2H),1.54(s,6H).

[0138] (2) Synthesis of Intermediate 13-2

[0139] The synthesis method refers to intermediate 1-2. 1 H NMR(400MHz, CDCl3):7.81(d,J=2.0Hz,1H),7.70(t,J=1.2Hz,1H),7.63-7.65(m,1H),7.53-7.56(m, 1H),7.40-7.46(m,3H),7.29-7.38(m,4H),7.11(dd,J=13.2,20.0Hz,2H),1.52(s,6H),1.24(s,12H).

[0140] (3) Synthesis of Compound 13

[0141] The synthesis method refers to compound 1. 1 H NMR(400MHz, CDCl3):8.14-8.18(m,4H),8.02(d,J=1.6Hz,1H),7.92(d,J=1.6Hz,1H),7.71-7.73 (m,1H),7.54-7.68(m,6H),7.28-7.48(m,17H),7.10(s,2H),1.55(s,6H).HRMS(ESI,m / z):[M+H] + calcd for:C 55 H 39 O,715.2995,found,715.2992.Anal.:calcd:C,92.40;H,5.36;O,2.24;found:C,92.26;H,5.48;O,2.18.

[0142] Example 5 Synthesis of Compound 18

[0143]

[0144] (1) Synthesis of Intermediate 18-1

[0145] The synthesis method refers to intermediate 1-1. 1 H NMR(400MHz, CDCl3):8.03-8.06(m,1H),7.91(d,J=1.6Hz,1H),7.63(t,J=1.6 Hz,1H),7.57-7.60(m,1H),7.33-7.51(m,7H),7.14(dd,J=13.2,17.2Hz,2H).

[0146] (2) Synthesis of Intermediate 18-2

[0147] The synthesis method refers to intermediate 1-2. 1 H NMR(400MHz, CDCl3):7.98-8.01(m,1H),7.90(d,J=1.6Hz,1H),7.70(t,J=1.6Hz,1H),7.63-7.65(m,1H) ,7.57-7.59(m,1H),7.37-7.51(m,4H),7.28-7.33(m,2H),7.13(dd,J=13.2,17.6Hz,2H),1.24(s,12H).

[0148] (3) Synthesis of Compound 18

[0149] The synthesis method refers to compound 1. 1 H NMR (400MHz, CDCl3): 8.14-8.18(m,4H),8.07-8.10(m,1H),8.01-8.03(m,1H),7.93(d,J=1.6Hz,1H),7.79(d,J=1.6Hz,1H),7.68(d ,J=1.6Hz,1H),7.57-7.63(m,5H),7.29-7.51(m,15H),7.26(d,J=6.0Hz,1H),7.13(dd,J=12.8,27.6Hz,2H).HRMS(ESI,m / z):[M+H] + calcd for:C 52 H 33 O2,689.2475,found,689.2477.Anal.:calcd:C,90.67;H,4.68;O,4.65;found:C,90.59;H,4.77;O,4.53.

[0150] Example 6 Synthesis of Compound 23

[0151]

[0152] (1) Synthesis of Intermediate 23-1

[0153] The synthesis method refers to intermediate 1-1. 1 H NMR(400MHz, CDCl3)δ:8.04-8.08(m,1H),7.88-7.91(m,1H),7.75-7.78(m,1H),7.64-7 .66(m,1H),7.48-7.52(m,1H),7.35-7.44(m,6H),7.28-7.32(m,1H),7.16-7.21(m,1H).

[0154] (2) Synthesis of Intermediate 23-2

[0155] The synthesis method is the same as that of intermediate 1-2. 1 H NMR(400MHz, CDCl3):8.06-8.10(m,1H),7.88-7.92(m,1H),7.80-7.82(m,1H),7.73(t,J=1.6Hz,1H),7.6 3-7.65(m,1H),7.46-7.49(m,1H),7.31-7.44(m,5H),7.17-7.21(m,1H),7.08-7.12(m,1H),1.24(s,12H).

[0156] (3) Synthesis of Compound 23

[0157] The synthesis method is the same as compound 1. 1 H NMR(400MHz, CDCl3):8.14-8.18(m,4H),8.04-8.06(m,2H),7.91-7.93(m,1H),7.86-7.88(m,1H),7.69-7.74 (m,2H),7.53-7.62(m,4H),7.34-7.47(m,16H),7.28-7.33(m,1H),7.10-7.15(m,1H).HRMS(ESI,m / z):[M+H] + calcd for:C 52 H 33 OS,705.2247,found,705.2242.Anal.:calcd:C,88.61;H,4.58;O,2.27;S,4.55;found:C,88.52;H,4.65;O,2.15;S,4.59.

[0158] Application Example 1

[0159] Preparation of organic electroluminescent devices, the structural diagram is shown in Figure 1 The specific device structure is as follows: glass / anode (ITO) / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / light-emitting layer (host material BH: blue light-emitting material BD) / hole blocking layer (HBL) / electron transport layer / electron injection layer (Liq) / cathode (Al).

[0160] 1) A transparent conductive ITO glass substrate 110 (with an anode 120 thereon, China Southern Glass Group Co., Ltd.) was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, and then washed in ethanol, acetone, and deionized water in sequence. It was baked in a clean environment to completely remove moisture, cleaned with ultraviolet photosynthetic ozone, and then treated with oxygen plasma for 30 seconds.

[0161] 2) The glass substrate with the anode is placed in a vacuum chamber, evacuated, and HIL (10 nm) is evaporated on the ITO as the hole injection layer 130 at a deposition rate of 0.1 nm / s.

[0162] 3) Compound HTL is evaporated on the hole injection layer to form a hole transport layer 140 with a thickness of 100 nm. The evaporation rate is 0.1 nm / s.

[0163] 4) TCTA was evaporated to form a 5 nm thick electron blocking layer (EBL) 150 at an evaporation rate of 0.1 nm / s.

[0164] 5) Compound 1 was evaporated on the electron blocking layer to form the light-emitting layer 160 with a thickness of 25 nm, and the evaporation rate was 0.1 nm / s.

[0165] 6) HB was evaporated on the light-emitting layer to form a 10 nm thick hole blocking layer 170 at a deposition rate of 0.1 nm / s. 7) ET was evaporated on the light-emitting layer to form an electron transport layer 180 at a deposition rate of 0.1 nm / s.

[0166] 8) 1 nm Liq was evaporated to form the electron injection layer 190 .

[0167] 9) 120 nm Al was evaporated to form the device cathode 200.

[0168] Application Example 2

[0169] The only difference from Application Example 1 is that Compound 6 is used in the light-emitting layer (160).

[0170] Application Example 3

[0171] The only difference from Application Example 1 is that Compound 11 is used in the light-emitting layer (160).

[0172] Application Example 4

[0173] The only difference from Application Example 1 is that Compound 13 is used in the light-emitting layer (160).

[0174] Application Example 5

[0175] The only difference from Application Example 1 is that Compound 18 is used in the light-emitting layer (160).

[0176] Application Example 6

[0177] The only difference from Application Example 1 is that Compound 23 is used in the light-emitting layer (160).

[0178] Comparative Example 1

[0179] The only difference from Application Example 1 is that the light-emitting layer (160) uses compound BH-1.

[0180] Comparative Example 2

[0181] The only difference from Application Example 1 is that the light-emitting layer (160) uses compound BH-2.

[0182] The structural formulas of the raw materials used in the above application examples and comparative examples are as follows:

[0183]

[0184] The above organic materials are all existing known materials and are purchased from the market.

[0185] The prepared device was tested using a Photo Research PR650 spectrometer at 1000 cd m -2 The operating voltage and external quantum efficiency under brightness. The device life service life measurement system is at 10mA / cm 2 The time it takes for the brightness to decay to 90% is measured under dark conditions at a given current density. The comparative examples and device examples above were all produced and tested from the same batch. Using the operating voltage, external quantum efficiency, and lifetime of device comparative example 1 as a benchmark (denoted as 1), the corresponding indicators for device comparative example 2 and application examples 1 to 6 were calculated, as shown in Table 2.

[0186] Table 2 Test results of organic electroluminescent devices

[0187]

[0188]

[0189] It can be seen from the experimental data in Table 2 that the compound containing anthracene and dibenzofuran provided by the present invention can be used as a blue light emitting material in an organic electroluminescent device.

[0190] Compared to devices in Comparative Examples 1 and 2, organic electroluminescent devices prepared using the anthracene- and dibenzofuran-containing organic electronic materials of the present invention exhibited reduced operating voltages and improved external quantum efficiencies. These data demonstrate the excellent performance of the anthracene- and dibenzofuran-containing organic electronic materials of the present invention as blue-light emitting materials in organic light-emitting devices.

[0191] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A blue light-emitting material containing anthracene and dibenzofuran, having a structure shown in Formula I: In formula I, Ar is phenyl; L is a phenyl group; A is an oxygen atom, a sulfur atom, 2. The method for preparing the blue light-emitting material containing anthracene and dibenzofuran according to claim 1, comprising the following steps: A compound having a structure represented by formula a is subjected to a Heck coupling reaction with a compound having a structure represented by formula b to obtain a compound having a structure represented by formula c; A compound having a structure shown in formula c is subjected to a Miyaura borylation reaction with pinacol diboron to obtain a compound having a structure shown in formula d; A compound having a structure represented by formula e is subjected to a coupling reaction with a compound having a structure represented by formula f to obtain a compound having a structure represented by formula g; The compound having the structure shown in formula g is subjected to bromination reaction with Br2 to obtain a compound having the structure shown in formula h: The compound having the structure shown in formula d is subjected to a Suzuki coupling reaction with the compound having the structure shown in formula h to obtain a compound having the structure shown in formula I.

3. The preparation method according to claim 2, characterized in that The Heck coupling reaction is carried out under the conditions of a base reagent and a catalyst, wherein the catalyst includes palladium acetate; The temperature of the Heck coupling reaction is 100-120° C., and the time is 5-8 hours.

4. The preparation method according to claim 2, characterized in that The Miyaura borylation reaction is carried out under the conditions of an alkaline reagent and a catalyst, wherein the catalyst includes palladium acetate; The temperature of the Miyaura boronation reaction is 100-120° C., and the time is 5-8 hours.

5. The preparation method according to claim 2, characterized in that The coupling reaction is carried out under the conditions of an alkaline reagent and a catalyst, wherein the catalyst includes palladium acetate; The coupling reaction temperature is 70-80°C and the time is 3-5h; The bromination reaction temperature is room temperature and the time is 5 to 8 hours.

6. The preparation method according to claim 2, characterized in that The Suzuki coupling reaction is carried out under the conditions of an alkaline reagent and a catalyst, wherein the catalyst includes palladium acetate; The temperature of the Suzuki coupling reaction is 70-80° C., and the reaction time is 5-8 hours.

7. Use of the blue light-emitting material containing anthracene and dibenzofuran according to claim 1 or the blue light-emitting material containing anthracene and dibenzofuran prepared by the preparation method according to any one of claims 2 to 6 in an organic electroluminescent device.

8. An organic electroluminescent device comprising an anode, a cathode and an organic layer, characterized in that: The organic layer comprises one or more of a light-emitting layer, a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer or an electron transport layer; At least one of the organic layers contains the blue light-emitting material containing anthracene and dibenzofuran according to claim 1 or the blue light-emitting material containing anthracene and dibenzofuran prepared by the preparation method according to any one of claims 2 to 6.

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