A kind of luminescence auxiliary material and its preparation method and application

Abstract

The present invention discloses a luminescent auxiliary material and a preparation method and application thereof, and relates to the field of organic photoelectric materials. The general molecular structure formula thereof is represented by Formula I: #imgabs0# wherein in Formula I, X is selected from any one of O, ‑NR1, ‑C(R2)(R3)‑, S; Ring A represents a substituted or unsubstituted C6-C30 aryl group, and A is cyclic with a benzene ring; R1 represents a substituted or unsubstituted aryl group with 6-30 carbon atoms, a substituted or unsubstituted 3-30 heteroaryl group; R2-R3 each independently represents a substituted or unsubstituted alkyl group with 1-10 carbon atoms, etc.; Ar1 ​​and Ar2 represent a substituted or unsubstituted cycloalkyl group with 3-20 carbon atoms, etc. The present invention provides a luminescent auxiliary material, which can significantly improve the life of a blue light device, and at the same time, the luminous efficiency, BI value, and driving voltage are also improved to a certain extent.

Description

Technical Field

[0001] The present invention relates to the field of organic photoelectric materials, and more specifically to a luminescent auxiliary material and a preparation method and application thereof. Background Art

[0002] Since 2000, organic electroluminescent devices (OLEDs) have received great attention. With rapid development, they have been widely used in display, lighting and other fields due to their advantages such as self-luminescence, high luminous efficiency, full-color display, low power consumption and low driving voltage. Organic electroluminescence uses the optoelectronic functional characteristics of organic semiconductor materials to directly convert electrical energy into light energy. It belongs to the carrier injection type of luminescence. The holes injected from the anode and the electrons injected from the cathode are combined in the light-emitting layer to form excitons, and release energy in the form of light energy. OLED devices are structurally divided into single-layer device structures, double-layer device structures, three-layer and multi-layer device structures. The most widely used one is the three-layer device structure, which has multiple functional layers such as electron transport layer, light-emitting layer and hole transport layer at the same time. The three functional layers perform their respective functions to optimize their performance.

[0003] The hole transport layer (HTL) is responsible for regulating the injection speed and amount of holes. However, most of the current hole transport layer materials will cause thermal stress between the anode and the hole injection layer when the OLED is driven at high current, and the thermal stress significantly reduces the service life of the device. Since the organic materials used in the hole transport region have very high hole mobility, the hole-electron charge balance may be destroyed and the quantum efficiency (cd / A) may be reduced.

[0004] In order to solve the above problems, a luminescent auxiliary layer is generally added between the hole transport layer and the light-emitting layer (i.e., the multi-layer hole transport layer mentioned above is set) to improve the device life and efficiency. The luminescent auxiliary layer can increase the hole utilization rate, thereby improving the luminous efficiency and life, and reducing the driving voltage. However, there are fewer materials for the luminescent auxiliary layer and it faces the problem of unclear gain effect. Therefore, it is urgent to develop organic functional materials with higher performance. Summary of the invention

[0005] In view of this, the present invention provides a luminescent auxiliary material, which can significantly improve the life of a blue light device. At the same time, the luminous efficiency, BI value, and driving voltage are also improved to a certain extent.

[0006] In order to achieve the above object, the present invention adopts the following technical solution:

[0007] A luminescence auxiliary material, the molecular structure of which is represented by Formula I:

[0008]

[0009] Wherein, in the formula I, X is selected from any one of O, -NR1, -C(R2)(R3)-, S;

[0010] Ring A represents a substituted or unsubstituted C6-C30 aryl group, A is cyclically coupled to the benzene ring, and A can be cyclically coupled to the 1,2 position, 2,3 position, or 3,4 position of the benzene ring;

[0011] R1 represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted 3 to 30-membered heteroaryl group;

[0012] R2-R3 each independently represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted 3 to 30-membered heteroaryl group;

[0013] Ar1 and Ar2 represent one or more of a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 3 to 30 carbon atoms, wherein the heteroatom is N, O, S, Si, P, or Se; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms, wherein the heteroatom is N, O, S, Si, P, or Se; a substituted or unsubstituted fused ring group having 10 to 30 carbon atoms, or a substituted or unsubstituted spiro ring group having 5 to 30 carbon atoms.

[0014] Preferably, the formula I is represented by the structure shown below:

[0015]

[0016] Preferably, the ring B is selected to be phenyl; and the ring A is selected to be phenyl.

[0017] Preferably, R1 is selected from any one of phenyl, naphthyl, biphenyl, phenanthryl, carbazolyl, fluorenyl, dimethylfluorenyl, terphenyl, benzofuran, benzothiophene, and pyridyl; and R2-R3 are selected from any one of methyl, ethyl, phenyl, methylbenzene, biphenyl, and naphthyl.

[0018] Preferably, Ar1 and Ar2 are connected to N at any connectable position, and Ar1 and Ar2 are selected from the following groups:

[0019]

[0020] Preferably, the formula Ia is selected as the following structure:

[0021]

[0022] Preferably, the formula Ib is selected as the following structure:

[0023]

[0024] Preferably, ring A, R1, Ar1, and Ar2 are the same as defined above.

[0025] In the present specification, the term "substituted or unsubstituted" means substituted by one, two or more substituents selected from the following: deuterium; a halogen group; a nitrile group; a silyl group; a boron group; a C1-C6 alkyl group; a C3-C10 cycloalkyl group; a C6-C18 aryl group; a C3-C30 heterocyclic group, or substituted by a substituent in which two or more substituents are connected among the substituents shown above, or having no substituent.

[0026] Furthermore, the light-emitting auxiliary material is preferably any one of the following structures, but is not limited thereto:

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039] Only some specific structural formulas are listed above, but the series of luminescent auxiliary materials protected by the present invention are not limited to the above molecular structures. Any simple transformation of the groups disclosed in the present invention and their substitution positions can obtain other specific molecular structures. The present invention will not list them in detail here, but they should all fall within the scope of protection of the present invention application.

[0040] A method for preparing the luminescent auxiliary material, the synthesis route of the formula I is as follows:

[0041] Step I:

[0042]

[0043] (1): Under nitrogen protection, reactant 1 (1.0 eq) was added to tetrahydrofuran, the temperature was lowered to -78°C, and n-BuLi (1.1-1.5 eq) was added dropwise to obtain a reaction solution of intermediate 2;

[0044] (2): Under nitrogen protection, the reaction solution of intermediate 2 (1.0 eq), reactant 3 (1-1.2 eq), palladium acetate (Pd(OAc )2 )(0.01-0.05eq), 2-cyclohexyl-2,4,6-triisopropylbiphenyl (X-Phos) (0.01-0.05eq), cesium carbonate (2.0-2.3eq) are dissolved in tetrahydrofuran, heated to 40-70°C, reacted for 2-8h, cooled to room temperature, H2O is added, separated, the organic layer is removed by a rotary evaporator, the obtained solid is heated and dissolved in toluene, passed through a silica gel funnel, and a mixture of methanol: dichloromethane in a volume ratio of 1:40-60 is used as a developing solvent, the obtained rotary evaporator is used to remove the solvent, and the obtained solid is dried to obtain intermediate 4;

[0045] (3): Under nitrogen protection, the intermediate 4 (1.0 eq) was dissolved in tetrahydrofuran (THF) and cooled to -78°C. n-BuLi (1.1-1.5 eq) was added dropwise and reacted for 0.5-4 h. The mixture was warmed to room temperature and added to the reactant 5 (1.1-1.4 eq) triisopropyl borate. The reaction was allowed to proceed overnight to fully react. Hydrochloric acid was added and the pH value of the solution was adjusted to 1-2 for acidification. The organic phases were separated and combined, and then dried over anhydrous magnesium sulfate. The solvent was removed using a rotary evaporator to obtain a solid organic matter. The solid organic matter was completely dissolved using dichloromethane and added dropwise to a petroleum ether solution. The mixture was stirred evenly to precipitate a precipitate. The solid was filtered to obtain the solid, which was then rinsed with anhydrous ethanol and petroleum ether in turn and dried to obtain the intermediate BI.

[0046] Step II:

[0047]

[0048] (1): Under the protection of nitrogen, reactant AI (1.0 eq), reactant BI (1.1-1.2 eq), tetrakis(triphenylphosphine)palladium (0.01-0.02 eq) and potassium carbonate (2.0-2.3 eq) are respectively added to a mixed solvent of toluene, ethanol and water in a volume ratio of 2-4:1:1, the temperature is raised to 80-100° C., and the reaction is carried out for 8-12 hours. After the reaction is completed, the mixture is cooled to room temperature, and after the solid is precipitated, it is filtered by suction, washed with water to remove salt, rinsed with ethanol, and the filter cake is dried and placed in 1,4-dioxane for recrystallization to obtain intermediate CI;

[0049] (2): Add intermediate CI (1.0 eq) and reactant DI (1.0-1.4 eq) to a reaction vessel and dissolve them in toluene, then add Pd2(dba)3 (0.01 eq), P(t-Bu)3 (0.02-0.04 eq), and t-BuONa (2.0-2.4 eq) under nitrogen protection; after addition, raise the reaction temperature to 105-115°C, and stir the mixture for 8-12 hours; use diatomaceous earth to filter to remove salt and catalyst, cool the filtrate to room temperature, then add distilled water to the filtrate for washing, retain the organic phase after separation, and extract the aqueous phase with ethyl acetate; then use magnesium sulfate to dry the organic layer, and use a rotary evaporator to remove the solvent; use dichloromethane and petroleum ether in a volume ratio of 1:1-9 as eluents, and purify the remaining substance by column chromatography to obtain intermediate EI;

[0050] (3): Add intermediate EI (1.0 eq) and reactant FI (1.0-1.4 eq) to a reaction vessel and dissolve them in toluene. Under nitrogen protection, add Pd2(dba)3 (0.01 eq), P(t-Bu)3 (0.02-0.04 eq), and t-BuONa (2.0-2.4 eq). After addition, raise the reaction temperature to 105-115°C and stir the mixture for 8-12 hours. Use diatomaceous earth to filter to remove salt and catalyst. After the filtrate is cooled to room temperature, add distilled water to the filtrate for washing. After separation, retain the organic phase and extract the aqueous phase with ethyl acetate. Use magnesium sulfate to dry the organic layer and use a rotary evaporator to remove the solvent. Use dichloromethane and petroleum ether in a volume ratio of 1:2-7 as eluents to purify the remaining substance by column chromatography to obtain a compound of general formula I.

[0051] Wherein, the ring A, ring B, X, Ar1, Ar2 are as defined in the above general formula I; Hal1 and Hal2 are selected from one of chlorine, bromine and iodine.

[0052] An application of a luminescence auxiliary material in an organic electroluminescent device, the organic electroluminescent device comprising a first electrode, a second electrode, and an organic layer arranged between the first electrode and the second electrode, the organic layer containing the luminescence auxiliary material.

[0053] It can be seen from the above technical solution that compared with the prior art, the present invention has the following beneficial effects:

[0054] The present invention uses naphthobenzofuran, naphthobenzothiophene, benzocarbazole, and benzofluorenyl as the skeleton and connects the aromatic amine group and the adamantyl group through a phenyl group with a bridging π group. Among them, adamantane has high spatial symmetry and a rigid structure. Introducing it into the condensed ring unit can effectively improve the thermal stability of the material. At the same time, the introduction of the adamantane building unit significantly improves the physical and chemical properties of the material, which is beneficial to improving the device performance and extending the device life.

[0055] The aromatic amine group gives it a strong hole transport ability. The triarylamine structure can reduce the crystallinity of the molecule, reduce the planarity of the molecule, and prevent the molecule from moving on the plane. At the same time, the high hole transport rate can reduce the driving voltage of the device and improve the efficiency and life of the organic electroluminescent device. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.

[0057] Figure 1 The attached figure is a hydrogen nuclear magnetic resonance spectrum of compound 2 obtained in Example 1 of the present invention. DETAILED DESCRIPTION

[0058] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0059] Example 1

[0060] Synthesis of compound 2

[0061] The synthetic route of reactant B-2 is as follows:

[0062]

[0063] CAS: Reactant b-1: 397243-08-2

[0064] CAS: Reactant b-3: 13101-40-1

[0065] Step 1:

[0066] Under nitrogen protection, reactant b-1 (300 mmol) was added to tetrahydrofuran, the temperature was lowered to -78°C, and n-BuLi (330 mmol) was slowly added dropwise to obtain a reaction solution of intermediate b-2;

[0067] Step 2:

[0068] Under nitrogen protection, the reaction solution containing intermediate b-2 (300 mmol), reactant b-3 (360 mmol), palladium acetate (Pd(OAc)2) (3 mmol), 2-cyclohexyl-2,4,6-triisopropylbiphenyl (X-Phos) (6 mmol), and cesium carbonate (630 mmol) were dissolved in 2100 mL of tetrahydrofuran, heated to 50°C, reacted for 4 hours, cooled to room temperature, added H2O, separated, and the organic layer was removed by a rotary evaporator. The obtained solid was heated and dissolved with toluene, passed through a silica gel funnel while hot, and methanol: dichloromethane (volume ratio of 1: (40-60) was used as a developing solvent. The obtained rotary evaporator was used to remove the solvent, and the obtained solid was dried to obtain intermediate b-4 (36.17 g, Mw: 325.88, yield: 37%);

[0069] Step 3:

[0070] Under nitrogen protection, the intermediate b-4 (105 mmol) was dissolved in 1050 ml of THF and cooled to -78 ° C, and n-BuLi (115.5 mmol) was slowly added dropwise, reacted for 2 hours, and warmed to room temperature. The reactant b-5 (126 mmol) (triisopropyl borate) was added to a mixed solvent, and fully reacted overnight. An appropriate amount of hydrochloric acid was added to adjust the pH value of the solution to between 1 and 2 for acidification. After separation, the organic phase was combined and dried with anhydrous magnesium sulfate. The remaining substance was purified by column chromatography using dichloromethane and petroleum ether in a volume ratio of 1: (2-7) as a developing solvent, and the obtained organic phase was desolventized with a rotary evaporator to obtain a solid organic matter. Use a small amount of dichloromethane to completely dissolve the solid organic matter, then slowly add it dropwise to the petroleum ether solution and stir evenly. A precipitate will be precipitated and the solid will be filtered out. It will be rinsed with anhydrous ethanol and petroleum ether in turn and dried to obtain reactant B-2 (25.97 g, Mw: 291.00, yield: 85%).

[0071]

[0072] CAS: Reactant A-2: 1846601-95-3

[0073] CAS: Reactant D-2: 1392267-83-2

[0074] Step 1:

[0075] Under the protection of nitrogen, reactant A-2 (80 mmol), reactant B-2 (88 mmol), tetrakis(triphenylphosphine)palladium (0.8 mmol) and potassium carbonate (168 mmol) were added to a mixed solvent of toluene (450 mL), ethanol (150 mL) and water (150 mL), respectively, and the temperature was raised to 90°C, and the reaction was carried out for 10 hours. After the reaction was completed, the mixture was cooled to room temperature, and after the solid was precipitated, it was filtered by suction, and then washed with water to remove the salt, and then rinsed with a small amount of ethanol, the filter cake was dried, and placed in 1,4-dioxane for recrystallization to obtain the compound shown in intermediate C-2 (22.61 g, Mw: 463.33, yield: 61%);

[0076] Step 2:

[0077] After adding intermediate C-2 (45 mmol) and reactant D-2 (54 mmol) to a reaction vessel and dissolving them in toluene, Pd2(dba)3 (0.45 mol), P(t-Bu)3 (0.9 mmol), and t-BuONa (99 mmol) were added under nitrogen protection; after the addition, the reaction temperature was slowly raised to 105°C, and the mixture was stirred for 10 hours; diatomaceous earth was used for hot filtration to remove salts and catalysts, and the filtrate was cooled to room temperature, and then distilled water was added to the filtrate for washing, and the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layer was dried with magnesium sulfate, and the solvent was removed with a rotary evaporator; using dichloromethane and petroleum ether in a volume ratio of 1: (1-9) as a developing agent, the remaining substance was purified by column chromatography to obtain compound intermediate E-2 (23.61 g, Mw: 596.15, yield: 88%);

[0078] Step 3:

[0079] After adding intermediate E-2 (35 mmol) and reactant F-2 (42 mmol) to a reaction vessel and dissolving them in toluene, Pd2(dba)3 (0.35 mmol), P(t-Bu)3 (0.84 mmol), and t-BuONa (80.5 mmol) were added under nitrogen protection; after the addition, the reaction temperature was slowly raised to 110°C, and the mixture was stirred for 9 hours; diatomaceous earth was used for hot filtration to remove salts and catalysts, and the filtrate was cooled to room temperature, and then distilled water was added to the filtrate for washing, and the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layer was dried with magnesium sulfate, and the solvent was removed with a rotary evaporator; the remaining substance was purified by column chromatography using dichloromethane and petroleum ether in a volume ratio of 1: (2-7) as a developing solvent to obtain compound 2 (22.26 g, yield: 85%);

[0080] The yield in each of the above steps is the fractional yield of the corresponding step.

[0081] Characterization:

[0082] HPLC purity: >99.8%.

[0083] Mass spectrometry test: theoretical value is 747.98; tested value is 748.22.

[0084] Elemental Analysis:

[0085] Theoretical values: C, 89.92; H, 6.06; N, 1.87; O, 2.14

[0086] Test values: C, 89.74; H, 6.21; N, 1.92; O, 2.21

[0087] The H NMR spectrum of compound 2 is shown in the attached figure. Figure 1 shown.

[0088] Example 2

[0089] Synthesis of compound 83

[0090]

[0091] CAS: Reactant A-83: 1256544-20-3

[0092] CAS: Reactant F-83: 86-76-0

[0093] Step 1:

[0094] Under the protection of nitrogen, reactant A-83 (80 mmol), reactant B-83 (88 mmol), tetrakis(triphenylphosphine)palladium (0.8 mmol) and potassium carbonate (168 mmol) were added to a mixed solvent of toluene (450 mL), ethanol (150 mL) and water (150 mL), respectively, and the temperature was raised to 90°C, and the reaction was carried out for 10 hours. After the reaction was completed, the mixture was cooled to room temperature, and after the solid was precipitated, it was filtered by suction, and then washed with water to remove the salt, and then rinsed with a small amount of ethanol, the filter cake was dried, and placed in 1,4-dioxane for recrystallization to obtain the compound represented by intermediate C-83 (21.50 g, Mw: 463.28, yield: 58%);

[0095] Step 2:

[0096] After adding intermediate C-83 (45 mmol) and reactant D-83 (54 mmol) to a reaction vessel and dissolving them in toluene, Pd2(dba)3 (0.45 mol), P(t-Bu)3 (0.9 mmol), and t-BuONa (99 mmol) were added under nitrogen protection; after the addition, the reaction temperature was slowly raised to 105°C, and the mixture was stirred for 10 hours; diatomaceous earth was used for hot filtration to remove salts and catalysts, and after the filtrate was cooled to room temperature, distilled water was then added to the filtrate for washing, and after separation, the organic phase was retained, and the aqueous phase was extracted with ethyl acetate; the combined organic layer was then dried with magnesium sulfate, and the solvent was removed with a rotary evaporator; the remaining substance was purified by column chromatography using dichloromethane and petroleum ether in a volume ratio of 1:(1-9) as a developing solvent to obtain compound intermediate E-83 (22.26 g, Mw: 596.11, yield: 83%);

[0097] Step 3:

[0098] After adding intermediate E-83 (35 mmol) and reactant F-83 (42 mmol) into a reaction vessel and dissolving them in toluene, Pd2 (dba )3 (0.35mmol), P(t-Bu)3(0.84mmol), t-BuONa(80.5mmol); after adding, the reaction temperature was slowly raised to 110°C, and the mixture was stirred for 9h; diatomaceous earth was used for hot filtration to remove salt and catalyst, and the filtrate was cooled to room temperature, and then distilled water was added to the filtrate for washing, and the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layer was dried with magnesium sulfate, and the solvent was removed with a rotary evaporator; the remaining substance was purified by column chromatography using dichloromethane and petroleum ether in a volume ratio of 1:(2-7) as a developing solvent to obtain compound 83 (22.95g, yield: 86%);

[0099] The yield in each of the above steps is the fractional yield of the corresponding step.

[0100] Characterization:

[0101] HPLC purity: >99.7%.

[0102] Mass spectrometry test: theoretical value is 761.97; tested value is 762.37.

[0103] Elemental Analysis:

[0104] Theoretical values: C, 88.27; H, 5.69; N, 1.84; O, 4.20

[0105] Test values: C, 88.14; H, 5.77; N, 1.89; O, 4.24

[0106] Example 3

[0107] Synthesis of compound 162

[0108]

[0109] CAS: Reactant A-162: 1268271-78-8

[0110] CAS: Reactant D-162: 108714-73-4

[0111] CAS: Reactant F-162: 50548-45-3

[0112] Step 1:

[0113] Under the protection of nitrogen, reactant A-162 (80 mmol), reactant B-162 (88 mmol), tetrakis(triphenylphosphine)palladium (0.8 mmol) and potassium carbonate (168 mmol) were added to a mixed solvent of toluene (450 mL), ethanol (150 mL) and water (150 mL), respectively, and the temperature was raised to 90°C, and the reaction was carried out for 10 hours. After the reaction was completed, the mixture was cooled to room temperature, and after the solid was precipitated, it was filtered by suction, and then washed with water to remove salt, and then rinsed with a small amount of ethanol, the filter cake was dried, and placed in 1,4-dioxane for recrystallization to obtain the compound represented by intermediate C-162 (25.84 g, Mw: 538.30, yield: 60%);

[0114] Step 2:

[0115] After adding intermediate C-162 (45 mmol) and reactant D-162 (54 mmol) to a reaction vessel and dissolving them in toluene, Pd2(dba)3 (0.45 mol), P(t-Bu)3 (0.9 mmol), and t-BuONa (99 mmol) were added under nitrogen protection; after the addition, the reaction temperature was slowly raised to 105°C, and the mixture was stirred for 10 hours; diatomaceous earth was used for hot filtration to remove salts and catalysts, and after the filtrate was cooled to room temperature, distilled water was then added to the filtrate for washing, and after separation, the organic phase was retained, and the aqueous phase was extracted with ethyl acetate; the combined organic layer was then dried with magnesium sulfate, and the solvent was removed with a rotary evaporator; the remaining substance was purified by column chromatography using dichloromethane and petroleum ether in a volume ratio of 1:(1-9) as a developing solvent to obtain compound intermediate E-162 (27.20 g, Mw: 711.03, yield: 85%);

[0116] Step 3:

[0117] After adding intermediate E-162 (35 mmol) and reactant F-162 (42 mmol) dissolved in toluene into the reaction container, Pd2(dba)3 (0.35 mmol), P(t-Bu)3 (0.84 mmol), t-BuONa (80.5 mmol) were added under nitrogen protection; after the addition, the reaction temperature was slowly raised to 110°C, and the mixture was stirred for 9 hours; diatomaceous earth was used for hot filtration to remove salt and catalyst, and the filtrate was cooled to room temperature, and then distilled water was added to the filtrate for washing, and the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layer was dried with magnesium sulfate, and the solvent was removed with a rotary evaporator; the remaining substance was purified by column chromatography using dichloromethane and petroleum ether in a volume ratio of 1: (2-7) as a developing solvent to obtain compound 162 (24.87 g, yield: 81%);

[0118] The yield in each of the above steps is the fractional yield of the corresponding step.

[0119] Characterization:

[0120] HPLC purity: >99.8%.

[0121] Mass spectrometry test: theoretical value is 877.14; tested value is 877.29.

[0122] Elemental Analysis:

[0123] Theoretical values: C, 89.01; H, 5.98; N, 3.19; O, 1.82

[0124] Test values: C, 88.84; H, 6.15; N, 3.22; O, 1.86

[0125] Example 4

[0126] Synthesis of compound 209

[0127]

[0128] CAS: Reactant b-8: 774608-49-0

[0129] Step 1:

[0130] Under nitrogen protection, add reactant b-6 (300 mmol) to tetrahydrofuran, cool to -78°C, and slowly drop n-BuLi (330 mmol) to obtain a reaction solution of intermediate b-7;

[0131] Step 2:

[0132] Under nitrogen protection, the reaction solution containing intermediate b-7 (300 mmol), reactant b-8 (360 mmol), palladium acetate (Pd(OAc)2) (3 mmol), 2-cyclohexyl-2,4,6-triisopropylbiphenyl (X-Phos) (6 mmol), and cesium carbonate (630 mmol) were dissolved in 2100 mL of tetrahydrofuran, heated to 50°C, reacted for 4 hours, cooled to room temperature, added H2O, separated, and the organic layer was removed by a rotary evaporator. The obtained solid was heated and dissolved with toluene, passed through a silica gel funnel while hot, and methanol: dichloromethane (volume ratio of 1: (40-60) was used as a developing solvent. The obtained rotary evaporator was used to remove the solvent, and the obtained solid was dried to obtain intermediate b-9 (33.23 g, Mw: 325.84, yield: 34%);

[0133] Step 3:

[0134] Under nitrogen protection, the intermediate b-9 (100 mmol) was dissolved in 1000 ml of THF and cooled to -78 ° C. n-BuLi (120 mmol) was slowly added dropwise, reacted for 2 hours, warmed to room temperature, and reacted in a mixed solvent of reactant b-10 (120 mmol) (triisopropyl borate) overnight to fully react, and an appropriate amount of hydrochloric acid was added to adjust the pH value of the solution to between 1 and 2 for acidification. After separation, the organic phase was combined and dried with anhydrous magnesium sulfate, and the remaining substance was purified by column chromatography using dichloromethane and petroleum ether in a volume ratio of 1: (2-7) as a developing solvent, and the obtained organic phase was desolventized with a rotary evaporator to obtain a solid organic matter. Use a small amount of dichloromethane to completely dissolve the solid organic matter, then slowly add it dropwise to the petroleum ether solution and stir evenly. A precipitate will be precipitated and the solid will be filtered out. It will be rinsed with anhydrous ethanol and petroleum ether in turn and dried to obtain the reactant B-209 (23.56 g, Mw: 290.89, yield: 81%).

[0135]

[0136] CAS: Reactant A-209: 1642127-11-4

[0137] Step 1:

[0138] Under the protection of nitrogen, reactant A-209 (80 mmol), reactant B-209 (88 mmol), tetrakis(triphenylphosphine)palladium (0.8 mmol) and potassium carbonate (168 mmol) were added to a mixed solvent of toluene (450 mL), ethanol (150 mL) and water (150 mL), respectively, and the temperature was raised to 90°C, and the reaction was carried out for 10 hours. After the reaction was completed, the mixture was cooled to room temperature, and after the solid was precipitated, it was filtered by suction, and then washed with water to remove salt, and then rinsed with a small amount of ethanol, the filter cake was dried, and recrystallized in 1,4-dioxane to obtain the compound represented by intermediate C-209 (22.98 g, Mw: 463.26, yield: 62%);

[0139] Step 2:

[0140] After adding intermediate C-209 (45 mmol) and reactant D-209 (54 mmol) to a reaction vessel and dissolving them in toluene, Pd2(dba)3 (0.45 mol), P(t-Bu)3 (0.9 mmol), and t-BuONa (99 mmol) were added under nitrogen protection; after the addition, the reaction temperature was slowly raised to 105°C, and the mixture was stirred for 10 hours; diatomaceous earth was used for hot filtration to remove salts and catalysts, and after the filtrate was cooled to room temperature, distilled water was then added to the filtrate for washing, and after separation, the organic phase was retained, and the aqueous phase was extracted with ethyl acetate; magnesium sulfate was then used to dry the combined organic layer, and a rotary evaporator was used to remove the solvent; dichloromethane and petroleum ether in a volume ratio of 1: (1-9) were used as developing agents, and the remaining substance was purified by column chromatography to obtain compound intermediate E-209 (23.89 g, Mw: 672.17, yield: 79%);

[0141] Step 3:

[0142] After adding intermediate E-209 (35 mmol) and reactant F-209 (42 mmol) dissolved in toluene into a reaction vessel, Pd2(dba)3 (0.35 mmol), P(t-Bu)3 (0.84 mmol), and t-BuONa (80.5 mmol) were added under nitrogen protection; after the addition, the reaction temperature was slowly raised to 110°C, and the mixture was stirred for 9 hours; diatomaceous earth was used for hot filtration to remove salt and catalyst, and the filtrate was cooled to room temperature, and then distilled water was added to the filtrate for washing, and the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layer was dried with magnesium sulfate, and the solvent was removed with a rotary evaporator; the remaining substance was purified by column chromatography using dichloromethane and petroleum ether in a volume ratio of 1: (2-7) as a developing solvent to obtain compound 209 (25.09 g, yield: 82%);

[0143] The yield in each of the above steps is the fractional yield of the corresponding step.

[0144] Characterization:

[0145] HPLC purity: >99.7%.

[0146] Mass spectrometry test: theoretical value is 874.14; tested value is 874.32.

[0147] Elemental Analysis:

[0148] Theoretical values: C, 90.69; H, 5.88; N, 1.60; O, 1.83

[0149] Test values: C, 90.53; H, 6.01; N, 1.64; O, 1.87

[0150] Example 5

[0151] Synthesis of compound 217

[0152]

[0153] CAS: Reactant b-13: 148836-41-3

[0154] Step 1:

[0155] Under nitrogen protection, add reactant b-11 (300 mmol) to tetrahydrofuran, cool to -78°C, and slowly drop n-BuLi (330 mmol) to obtain a reaction solution of intermediate b-12;

[0156] Step 2:

[0157] Under nitrogen protection, the reaction solution containing intermediate b-12 (300 mmol), reactant b-13 (360 mmol), palladium acetate (Pd(OAc)2) (3 mmol), 2-cyclohexyl-2,4,6-triisopropylbiphenyl (X-Phos) (6 mmol), and cesium carbonate (630 mmol) were dissolved in 2100 mL of tetrahydrofuran, heated to 50°C, reacted for 4 hours, cooled to room temperature, added H2O, separated, and the organic layer was removed by a rotary evaporator. The obtained solid was heated and dissolved with toluene, passed through a silica gel funnel while hot, and methanol: dichloromethane (volume ratio of 1: (40-60) was used as a developing solvent. The obtained rotary evaporator was used to remove the solvent, and the obtained solid was dried to obtain intermediate b-14 (35.21 g, Mw: 325.99, yield: 36%);

[0158] Step 3:

[0159] Under nitrogen protection, the intermediate b-14 (105 mmol) was dissolved in 1050 ml of THF and cooled to -78 ° C. n-BuLi (126 mmol) was slowly added dropwise, and the reaction was continued for 2 hours. The mixture was warmed to room temperature, and the reactant b-15 (126 mmol) (triisopropyl borate) was added to a mixed solvent, and the reaction was continued overnight. An appropriate amount of hydrochloric acid was added to adjust the pH value of the solution to between 1 and 2 for acidification. The organic phases were separated, and dried with anhydrous magnesium sulfate. The remaining substances were purified by column chromatography using dichloromethane and petroleum ether in a volume ratio of 1: (2-7) as the developing solvent. The obtained organic phase was desolventized by a rotary evaporator to obtain a solid organic matter. Use a small amount of dichloromethane to completely dissolve the solid organic matter, then slowly add it dropwise to the petroleum ether solution and stir evenly. A precipitate will be precipitated and the solid will be filtered out. It will be rinsed with anhydrous ethanol and petroleum ether in turn and dried to obtain the reactant B-217 (25.35 g, Mw: 290.85, yield: 83%).

[0160]

[0161] CAS: Reactant A-217: 1674334-94-1

[0162] Step 1:

[0163] Under the protection of nitrogen, reactant A-217 (80 mmol), reactant B-217 (88 mmol), tetrakis(triphenylphosphine)palladium (0.8 mmol) and potassium carbonate (168 mmol) were added to a mixed solvent of toluene (450 mL), ethanol (150 mL) and water (150 mL), respectively, and the temperature was raised to 90°C, and the reaction was carried out for 10 hours. After the reaction was completed, the mixture was cooled to room temperature, and after the solid was precipitated, it was filtered by suction, and then washed with water to remove the salt, and then rinsed with a small amount of ethanol, the filter cake was dried, and placed in 1,4-dioxane for recrystallization to obtain the intermediate C-217 (23.88 g, Mw: 489.30, yield: 61%);

[0164] Step 2:

[0165] After adding intermediate C-217 (45 mmol) and reactant D-217 (54 mmol) dissolved in toluene into a reaction vessel, Pd2(dba)3 (0.45 mol), P(t-Bu)3 (0.9 mmol), and t-BuONa (99 mmol) were added under nitrogen protection; after the addition, the reaction temperature was slowly raised to 105°C, and the mixture was stirred for 10 hours; diatomaceous earth was used for hot filtration to remove salt and catalyst, and the filtrate was cooled to room temperature, and then distilled water was added to the filtrate for washing, and the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layer was dried with magnesium sulfate, and the solvent was removed with a rotary evaporator; using dichloromethane and petroleum ether in a volume ratio of 1: (1-9) as a developing agent, the remaining substance was purified by column chromatography to obtain compound intermediate E-217 (24.50 g, Mw: 633.13, yield: 86%);

[0166] Step 3:

[0167] After adding intermediate E-217 (35 mmol) and reactant F-217 (42 mmol) dissolved in toluene into a reaction vessel, Pd2(dba)3 (0.35 mmol), P(t-Bu)3 (0.84 mmol), and t-BuONa (80.5 mmol) were added under nitrogen protection; after the addition, the reaction temperature was slowly raised to 110°C, and the mixture was stirred for 9 hours; diatomaceous earth was used for hot filtration to remove salt and catalyst, and the filtrate was cooled to room temperature, and then distilled water was added to the filtrate for washing, and the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layer was dried with magnesium sulfate, and the solvent was removed with a rotary evaporator; the remaining substance was purified by column chromatography using dichloromethane and petroleum ether in a volume ratio of 1: (2-7) as a developing solvent to obtain compound 217 (22.52 g, yield: 79%);

[0168] The yield in each of the above steps is the fractional yield of the corresponding step.

[0169] Characterization:

[0170] HPLC purity: >99.8%.

[0171] Mass spectrometry test: theoretical value is 814.13; tested value is 814.35.

[0172] Elemental Analysis:

[0173] Theoretical values: C, 91.47; H, 6.81; N, 1.72

[0174] Test value: C, 91.33; H, 6.95; N, 1.80

[0175] Embodiment 6-60

[0176] The following compounds were prepared by referring to the synthesis methods of Examples 1-5. The molecular formula and mass spectrum of the compounds are shown in Table 1:

[0177] Table 1 Molecular formula and mass spectrum of compounds of Examples 6-60

[0178]

[0179]

[0180]

[0181] Other compounds of the present invention can be obtained by referring to the synthesis methods of the above-mentioned embodiments, so they are not listed one by one here.

[0182] Another object of the present invention is to provide an organic electroluminescent device containing a light-emitting auxiliary material, comprising a first electrode, a second electrode arranged opposite to the first electrode, and at least one organic layer between the first electrode and the second electrode, wherein at least one of the organic layers contains the compound represented by formula I prepared by the present invention.

[0183] The organic light-emitting element of the present invention may have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting auxiliary layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc. as organic layers. However, the structure of the organic light-emitting element is not limited thereto, and may include fewer or more organic layers.

[0184] According to one embodiment of the present specification, the organic layer comprises a light-emitting auxiliary layer, and the light-emitting auxiliary layer comprises the compound represented by formula I prepared by the present invention.

[0185] When the organic light emitting element includes a plurality of organic layers, the organic layers may be formed of the same substance or different substances.

[0186] When manufacturing an organic light-emitting element, the compound represented by the above formula I can be formed into an organic layer by vacuum evaporation or solution coating, wherein the solution coating method includes spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying, roller coating, etc., but is not limited thereto.

[0187] The organic light emitting element of the present invention may be a top emission type, a bottom emission type or a bi-directional emission type depending on the materials used.

[0188] The device of the present invention can be used in organic light-emitting devices, organic solar cells, electronic paper, organic photoreceptors or organic thin film transistors.

[0189] The present invention provides a method for preparing an organic electroluminescent device, comprising the step of including the above-mentioned auxiliary luminescent material in the organic layer.

[0190] Application Example 1: Preparation of organic electroluminescent devices:

[0191] a. ITO anode: Wash the ITO (indium tin oxide)-Ag-ITO (indium tin oxide) glass substrate with a coating thickness of 150nm in distilled water twice, ultrasonically wash for 30 minutes, and then repeatedly wash it with distilled water twice, ultrasonically wash for 10 minutes. After washing, transfer it to a spin dryer for drying, and finally bake it in a vacuum oven at 220℃ for 2 hours. After baking, cool it down and it can be used. Use this substrate as the anode, use an evaporation machine to carry out the evaporation device process, and evaporate other functional layers on it in sequence.

[0192] b. HIL (hole injection layer): The hole injection layer materials HT-1 and P-dopant are vacuum evaporated at a deposition rate of 98:2, and the thickness is 10 nm;

[0193] c. HTL (hole transport layer): At a deposition rate of 100%, 120 nm of HT-1 was vacuum-deposited on the hole injection layer as a hole transport layer.

[0194] d. Light-emitting auxiliary layer: At a deposition rate of , 10 nm of the formula I provided in the above embodiment is vacuum-deposited on the hole transport layer as a light-emitting auxiliary layer;

[0195] e. EML (light-emitting layer): Then on the above-mentioned light-emitting auxiliary layer, The host material (Host) and dopant material (Dopant) with a thickness of 25nm were vacuum-deposited as the light-emitting layer. The chemical formulas of Host-1 and Dopant-1 are shown below. The evaporation rate ratio of Host-1 to Dopant-1 is 97:3.

[0196] f. HB (hole blocking layer): The hole blocking layer with a thickness of 5.0 nm was vacuum-deposited at a deposition rate of . Its chemical formula is shown below.

[0197] g. ETL (Electron Transport Layer): At a deposition rate of , ET-1 and Liq with a thickness of 35 nm were vacuum-deposited as an electron transport layer, and the chemical formula of ET-1 is shown below. The deposition rate ratio of ET-1 to Liq is 50:50.

[0198] h. EIL (electron injection layer): At a evaporation rate of , a 1.0 nm Yb film layer was evaporated to form an electron injection layer.

[0199] i. Cathode: The evaporation rate ratio is 1:9, and magnesium and silver are evaporated at 18nm, and the evaporation rate ratio is 1:9 to obtain an OLED device.

[0200] j. Light extraction layer: At a deposition rate of , CPL-1 with a thickness of 70 nm was vacuum-deposited on the cathode as a light extraction layer.

[0201] k. Package the substrate after evaporation. First, use the glue coating equipment to coat the cleaned cover with UV glue, then move the coated cover to the pressing section, place the evaporation-deposited substrate on the upper end of the cover, and finally bond the substrate and cover with the bonding equipment, and complete the light curing of the UV glue.

[0202] Device structure:

[0203] ITO / Ag / ITO / HT-1: P-dopant (10nm, 3%) / HT-1 (120nm) / Formula I (10nm) / Host-1: Dopant (2 5nm, 2%) / HB(5nm) / ET-1: Liq(35nm, 50%) / Yb(1nm) / Mg:Ag(18nm, 1:9) / CPL-1(70nm).

[0204]

[0205] Application Example 2-60:

[0206] The organic electroluminescent devices of Application Examples 2-60 were prepared according to the above-mentioned method for preparing an organic electroluminescent device, except that the compound 2 in Application Example 1 was replaced by corresponding compounds to form a light-emitting auxiliary layer.

[0207] Comparative Example 1

[0208] An organic electroluminescent device was prepared according to the above method for preparing an organic electroluminescent device containing a luminescent auxiliary material, except that the compound in Application Example 1 was replaced by Comparative Compound 1.

[0209] Comparative Example 2

[0210] An organic electroluminescent device was prepared according to the above method for preparing an organic electroluminescent device containing a luminescent auxiliary material, except that the compound in Application Example 1 was replaced by Comparative Compound 2.

[0211] Comparative Example 3

[0212] An organic electroluminescent device was prepared according to the above method for preparing an organic electroluminescent device containing a luminescent auxiliary material, except that the compound in Application Example 1 was replaced by Comparative Compound 3.

[0213] Comparative Example 4

[0214] An organic electroluminescent device was prepared according to the above method for preparing an organic electroluminescent device containing a luminescent auxiliary material, except that the compound in Application Example 1 was replaced by Comparative Compound 4.

[0215] Comparative Example 5

[0216] An organic electroluminescent device was prepared according to the above method for preparing an organic electroluminescent device containing a luminescent auxiliary material, except that the compound in Application Example 1 was replaced by Comparative Compound 5.

[0217] Comparative Example 6

[0218] An organic electroluminescent device was prepared according to the above method for preparing an organic electroluminescent device containing a luminescent auxiliary material, except that the compound in Application Example 1 was replaced by Comparative Compound 6.

[0219] Comparative Example 7

[0220] An organic electroluminescent device was prepared according to the above method for preparing an organic electroluminescent device containing a luminescent auxiliary material, except that the compound in Application Example 1 was replaced by Comparative Compound 7.

[0221] The structural formula of comparative compound 1-7 is as follows:

[0222]

[0223] The driving voltage, luminous efficiency, BI value and life of the organic electroluminescent devices obtained from the device application examples 1 to 60 and the device comparative examples 1 to 7 were characterized at a brightness of 1000 (nits). The test results are shown in Table 2 below:

[0224] Table 2 Luminous characteristics test results (brightness: 1000nits)

[0225]

[0226]

[0227] Those skilled in the art know that due to the microcavity effect, the luminous efficiency is greatly affected by the chromaticity, so the BI value is introduced as the basis for the efficiency of blue light luminescent materials, BI = luminous efficiency / CIEy.

[0228] The present invention uses naphthoxybenzofuran, naphthoxybenzothiophene, benzocarbazole and benzofluorenyl as the skeleton and connects the phenyl group with the aromatic amine group and the adamantyl group through the phenyl group with the bridging π group. Among them, adamantane has high spatial symmetry and rigid structure. Its introduction into the condensed ring unit can effectively improve the thermal stability of the material. At the same time, the introduction of the adamantane building unit significantly improves the physical and chemical properties of the material, which is beneficial to improving the device performance and extending the device life.

[0229] As can be seen from the table above, the performance of the light-emitting auxiliary material devices used in Comparative Examples 1-7 and Application Examples 1-60 has been significantly improved in lifespan, and the luminous efficiency, BI value, and driving voltage have also been improved to a certain extent.

[0230] From the experimental data, the main difference between compound 63 and comparative examples 5 and 6 is the use of adamantane, which extends the life of the blue light device by about 70 hours, an increase of about 14%. Compared with the comparative compounds, other compounds of the present invention containing adamantane generally increase the life by about 8-16%, which has achieved a significant improvement in the blue light life.

[0231] In this field, the problem of short life of blue light devices has always been one of the problems that technicians in this field need to solve urgently. The adamantane in the present invention can significantly improve the structural stability of the compound and significantly increase the life of the blue light device, which is conducive to application in actual production.

[0232] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

[0233] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A luminescent auxiliary material, characterized in that: Its molecular structure is represented by formula I: Wherein, in the formula I, X is selected from any one of O, -NR1, -C(R2)(R3)-, S; Ring A is selected to be phenyl, A is cyclically coupled to the benzene ring, and A can be cyclically coupled to the 1,2 position, 2,3 position, or 3,4 position of the benzene ring; The ring B is selected to be phenyl; R1 represents an unsubstituted aryl group having 6 to 30 carbon atoms or an unsubstituted 3 to 30-membered heteroaryl group; R2-R3 each independently represents an unsubstituted alkyl group having 1 to 10 carbon atoms, an unsubstituted aryl group having 6 to 30 carbon atoms, or an unsubstituted 3 to 30-membered heteroaryl group; Ar1 and Ar2 represent one or more of an unsubstituted cycloalkyl group having 3 to 20 carbon atoms, an unsubstituted heterocycloalkyl group having 3 to 30 carbon atoms, wherein the heteroatom is N, O, S, Si, P, or Se; an unsubstituted aryl group having 6 to 30 carbon atoms, an unsubstituted heteroaryl group having 3 to 20 carbon atoms, wherein the heteroatom is N, O, S, Si, P, or Se; an unsubstituted condensed ring group having 10 to 30 carbon atoms, and an unsubstituted spiro ring group having 5 to 30 carbon atoms.

2. A luminescence auxiliary material according to claim 1, characterized in that: The formula I is represented by the structure shown below:

3. A luminescence auxiliary material according to claim 1, characterized in that: The R1 is selected from any one of phenyl, naphthyl, biphenyl, phenanthryl, carbazolyl, fluorenyl, dimethylfluorenyl, terphenyl, benzofuran, benzothiophene, and pyridyl; and the R2-R3 are selected from any one of methyl, ethyl, phenyl, methylbenzene, biphenyl, and naphthyl.

4. A luminescence auxiliary material according to claim 1, characterized in that: Ar1 and Ar2 are connected to N at any connectable position, and Ar1 and Ar2 are selected from the following groups:

5. A luminescence auxiliary material according to claim 2, characterized in that: The formula Ia is selected as the following structure:

6. A luminescence auxiliary material according to claim 2, characterized in that: The formula Ib is selected as the following structure:

7. The luminescence auxiliary material according to any one of claims 1 to 6, characterized in that: The structure of Formula I comprises:

8. A method for preparing the luminescence auxiliary material according to claim 1, characterized in that: The synthetic route of formula I is as follows: Step I: (1): Under nitrogen protection, 1.0 eq of reactant 1 was added to tetrahydrofuran, the temperature was cooled to -78°C, and 1.1-1.5 eq of n-BuLi was added dropwise to obtain a reaction solution of intermediate 2; (2): Under nitrogen protection, 1.0 eq of the reaction solution of intermediate 2, 1-1.2 eq of reactant 3, 0.01-0.05 eq of palladium acetate Pd(OAc)2, 0.01-0.05 eq of 2-cyclohexyl-2,4,6-triisopropylbiphenyl X-Phos, and 2.0-2.3 eq of cesium carbonate are dissolved in tetrahydrofuran, the temperature is raised to 40-70°C, the reaction is carried out for 2-8 hours, the reaction is cooled to room temperature, H2O is added, the liquid is separated, the organic layer is removed by a rotary evaporator to remove the solvent, the obtained solid is dissolved by heating with toluene, passed through a silica gel funnel, and a mixture of methanol: dichloromethane in a volume ratio of 1:40-60 is used as a developing solvent, the obtained rotary evaporator is used to remove the solvent, and the obtained solid is dried to obtain intermediate 4; (3): Under nitrogen protection, 1.0 eq of intermediate 4 was dissolved in tetrahydrofuran (THF) and cooled to -78°C, 1.1-1.5 eq of n-BuLi was added dropwise, and the reaction was continued for 0.5-4 h. The mixture was warmed to room temperature, and 1.1-1.4 eq of reactant 5 was added to triisopropyl borate. The reaction was continued overnight until sufficient reaction occurred. Hydrochloric acid was added to adjust the pH value of the solution to 1-2 for acidification. The organic phases were separated, and then dried over anhydrous magnesium sulfate after combining the organic phases. The solvent was removed by a rotary evaporator to obtain a solid organic matter. The solid organic matter was completely dissolved with dichloromethane, and the solution was added dropwise to a petroleum ether solution. The mixture was stirred evenly to precipitate a precipitate. The solid was filtered to obtain the solid, and the solid was washed with anhydrous ethanol and petroleum ether in turn, and dried to obtain the intermediate BI. Step II: (1): Under the protection of nitrogen, 1.0 eq of reactant AI, 1.1-1.2 eq of reactant BI, 0.01-0.02 eq of tetrakis(triphenylphosphine)palladium and 2.0-2.3 eq of potassium carbonate are respectively added to a mixed solvent of toluene, ethanol and water in a volume ratio of 2-4:1:1, the temperature is raised to 80-100° C., the reaction is carried out for 8-12 hours, after the reaction is completed, the reaction is cooled to room temperature, and after the solid is precipitated, it is filtered by suction, washed with water to remove salt, rinsed with ethanol, the filter cake is dried, and placed in 1,4-dioxane for recrystallization to obtain intermediate CI; (2): After adding 1.0eq of intermediate CI and 1.0-1.4eq of reactant DI to a reaction vessel and dissolving them in toluene, 0.01eq of Pd2(dba)3, 0.02-0.04eq of P(t-Bu)3, and 2.0-2.4eq of t-BuONa were added under nitrogen protection; after the addition, the reaction temperature was raised to 105-115°C, and the mixture was stirred for 8-12 hours; diatomaceous earth was used for suction filtration to remove salt and catalyst, and after the filtrate was cooled to room temperature, distilled water was then added to the filtrate for washing, and after separation, the organic phase was retained, and the aqueous phase was extracted with ethyl acetate; the organic layer was then dried with magnesium sulfate, and the solvent was removed with a rotary evaporator; the remaining substance was purified by column chromatography using dichloromethane and petroleum ether in a volume ratio of 1:1-9 as eluent to obtain intermediate EI; (3): 1.0 eq of intermediate EI and 1.0-1.4 eq of reactant FI were added to a reaction vessel and dissolved in toluene. Under nitrogen protection, 0.01 eq of Pd2(dba)3, 0.02-0.04 eq of P(t-Bu)3, and 2.0-2.4 eq of t-BuONa were added. After the addition, the reaction temperature was raised to 105-115°C, and the mixture was stirred for 8-12 hours. The salt and catalyst were removed by filtration using diatomaceous earth. After the filtrate was cooled to room temperature, distilled water was added to the filtrate for washing. After separation, the organic phase was retained and the aqueous phase was extracted with ethyl acetate. The organic layer was dried with magnesium sulfate and the solvent was removed with a rotary evaporator. The remaining substance was purified by column chromatography using dichloromethane and petroleum ether in a volume ratio of 1:2-7 as eluent to obtain a compound of general formula I. Wherein, the ring A, ring B, X, Ar1, and Ar2 are as defined in the above general formula I; Hal1 and Hal2 are selected from one of chlorine, bromine, and iodine.

9. Application of a luminescent auxiliary material in an organic electroluminescent device, characterized in that: The organic electroluminescent device comprises a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises the luminescence auxiliary material according to any one of claims 1 to 7.

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