A light-emitting auxiliary layer material, a light-emitting device and a light-emitting apparatus

Abstract

The present application is applicable to the field of material technology, and provides a light-emitting auxiliary layer material, a light-emitting device and a light-emitting apparatus. The light-emitting auxiliary layer material provided in the present application can be simultaneously applied to red and green organic electroluminescent devices, effectively improving the lifespan and luminous efficiency of OLED devices, reducing the driving voltage, and meeting the requirements of panel manufacturers.

Description

Technical Field

[0001] The present application belongs to the field of material technology, and in particular relates to a light-emitting auxiliary layer material, a light-emitting device and a light-emitting apparatus. Background Art

[0002] Organic electroluminescent display (OLED) is an active light-emitting display device. It has the characteristics of self-luminescence, bright colors, thin thickness, light weight, fast response speed, wide viewing angle, low driving voltage, tolerance to harsh natural conditions, and can be made into flexible panels. At present, small and medium-sized OLED display screens have been widely used in high-end smartphones produced by Huawei, Xiaomi, Samsung and other companies. Obtaining the best luminous efficiency of the device under low operating voltage conditions is a common demand in the OLED field.

[0003] Organic electroluminescent devices generally have the following structure: an anode, a cathode, and an organic material layer between the two. In order to improve the efficiency and stability of organic EL elements, the organic material layer is composed of different functional layers, such as a hole injection layer (HIL), a hole transport layer (HTL), a light-emitting auxiliary layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer (ETL), and an electron injection layer (EIL).

[0004] The light-emitting auxiliary layer is arranged between the hole transport layer and the light-emitting layer, which can reduce the potential barrier between the hole transport layer and the light-emitting layer, reduce the driving voltage of the organic electroluminescent device, and further increase the utilization of holes, thereby improving the luminous efficiency and life of the device and reducing the driving voltage. However, there are few functional materials that can form the light-emitting auxiliary layer, especially the life and luminous efficiency of OLED are not significantly improved, so it is particularly important to develop higher performance organic functional materials to meet the requirements of panel manufacturers. Summary of the invention

[0005] The purpose of the present application is to provide a luminescent auxiliary layer material, aiming to solve the problem that the existing luminescent auxiliary layer materials have poor effects on improving device life and luminescent efficiency.

[0006] The present application is implemented as follows: a light-emitting auxiliary layer material, the structure of the light-emitting auxiliary layer material is shown in general formula I:

[0007]

[0008] Wherein in the general formula I, n is an integer selected from 1, 2, 3, 4;

[0009] R1 is arbitrarily substituted on the benzene ring; R1 is one of hydrogen, methyl, ethyl, propyl, isopropyl, and tert-butyl;

[0010] R2 is one of methyl, ethyl, propyl and isopropyl;

[0011] Ring A is a phenyl group fused to an adjacent benzene ring;

[0012] X is one of O, S, -C(CH3)2-;

[0013] Y is a single bond, one of O, S, -CR3R4-, and -NR5-;

[0014] Ar1 is independently selected from substituted or unsubstituted C6-C18 aryl, and substituted or unsubstituted heteroaryl having 3 to 18 ring carbon atoms.

[0015] Another object of the present application is a light-emitting device, which includes the light-emitting auxiliary layer material.

[0016] Another object of the present application is a light-emitting device, which includes the light-emitting auxiliary layer or the light-emitting device.

[0017] The light-emitting auxiliary layer material provided in the present application can be applied to both red and green organic electroluminescent devices, effectively improving the lifespan and luminous efficiency of OLED devices, reducing the driving voltage, and meeting the requirements of panel manufacturers. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 is the hydrogen nuclear magnetic resonance spectrum of compound 2 provided in Example 1 of the present application;

[0019] Figure 2 is the hydrogen nuclear magnetic resonance spectrum of compound 46 provided in Example 3 of the present application;

[0020] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of compound 76 provided in Example 4 of the present application. DETAILED DESCRIPTION

[0021] In order to make the purpose, technical solution and advantages of the present application more clearly understood, the present application is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0022] The present application provides a light-emitting auxiliary layer material, the structural formula of which is shown in the following general formula I:

[0023]

[0024] in,

[0025] n is an integer selected from 1, 2, 3, 4;

[0026] R1 is arbitrarily substituted on the benzene ring;

[0027] R1 is independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, tert-butyl;

[0028] R2 is independently selected from methyl, ethyl, propyl, isopropyl;

[0029] Ring A is a phenyl group fused to an adjacent benzene ring;

[0030] X is selected from O, S, -C(CH3)2-;

[0031] Y is selected from a single bond, O, S, -CR3R4-, -NR5-;

[0032] R3-R4 are independently selected from C1-C6 alkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted heteroaryl with 3-18 ring carbon atoms, wherein the heteroatom in the heteroaryl can be O, S, N:

[0033] R5 is independently selected from substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted heteroaryl having 3-18 ring carbon atoms, wherein the heteroatom in the heteroaryl may be O, S, or N;

[0034] Ar1 is selected from substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted heteroaryl having 3-18 ring carbon atoms;

[0035] Furthermore, Formula I has the structures shown in general formulas I-1 to I-5:

[0036]

[0037] n is selected from 1 and 2;

[0038] X is selected from O, -C(CH3)2-;

[0039] R3-R4 are each independently selected from methyl, ethyl, propyl, phenyl, naphthyl, phenanthryl, biphenyl, terphenyl, methylphenyl, pyridyl, phenylpyridyl;

[0040] R5 is independently selected from phenyl, naphthyl, methylphenyl, biphenyl, dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl;

[0041] Ar1 is independently selected from the following groups:

[0042]

[0043] Furthermore, the general formula I has the structures shown in formulas I-6 to I-11:

[0044]

[0045] 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.

[0046] Furthermore, the compounds represented by the general formula I can be specifically illustrated by the following compounds, but are not limited thereto.

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053] The light-emitting auxiliary layer material of the present application can be prepared by a synthesis method known to those skilled in the art. Alternatively, the following reaction process is preferably used for preparation.

[0054] The synthetic route of general formula I is as follows:

[0055] (1) When Y is a single bond:

[0056]

[0057] Step 1:

[0058] Add reactant BI (1.1-1.2eq) to the reaction vessel, add THF and stir until fully dissolved, replace with nitrogen three times, cool to -78°C, add n-BuLi (1.1-1.2eq) dropwise, stir for 2-4h, dissolve reactant AI (1.0eq) in tetrahydrofuran, add dropwise to the reaction system, after the addition is complete, warm to room temperature and stir for 6-10h; slowly add dilute hydrochloric acid to terminate the reaction, separate the liquids, collect the organic phase, extract the aqueous phase with dichloromethane three times, combine the organic phases, add anhydrous sodium sulfate to dry, remove the solvent by rotary evaporator to obtain a solid powder, and after the solid is dried, obtain the intermediate CI.

[0059] Step 2:

[0060] Under N2 protection, intermediate CI (1.0 eq) was added to the reaction vessel, dissolved in HOAC, heated to 100-105°C, H2SO4 was added dropwise, stirred for 1-2 hours, cooled to room temperature, saturated sodium bicarbonate solution was added to terminate the reaction, the liquids were separated, the aqueous phase was extracted with dichloromethane, the organic phase was collected, anhydrous magnesium sulfate was added for drying, the solvent was removed by a rotary evaporator, and the solid was dried to obtain intermediate DI.

[0061] Step 3:

[0062] Under N2 protection, add intermediate DI (1.0 eq) and reactant EI (1.1-1.4 eq) to a reaction vessel and dissolve in toluene, then add Pd2(dba)3 (0.01-0.03 eq), P(t-Bu)3 (0.05-0.1 eq), and t-BuONa (2.0-2.4 eq). After addition, heat to 105-115°C and react for 6-10 hours. Use diatomaceous earth to filter while hot to remove salt and catalyst. After the filtrate is cooled to room temperature, use a rotary evaporator to remove the solvent. After the solid is dried, pass through a silica gel funnel, use dichloromethane: petroleum ether volume ratio of 1: (1-4) as the eluent, remove the filtrate with a rotary evaporator, and dry the solid to obtain general formula I.

[0063] (2) When Y is not a single bond:

[0064]

[0065] Step 1:

[0066] Add reactant bI (1.1-1.2 eq) to a reaction vessel, add THF and stir until fully dissolved, replace with nitrogen three times, cool to -78°C, add n-BuLi (1.1-1.2 eq) dropwise, stir for 2-3 h, dissolve reactant aI (1.0 eq) in tetrahydrofuran, add dropwise to the reaction system, warm to room temperature and stir for 6-10 h after the addition is complete; slowly add dilute hydrochloric acid to terminate the reaction, separate the liquids, collect the organic phase, extract the aqueous phase with dichloromethane three times, combine the organic phases, add anhydrous sodium sulfate to dry, remove the solvent by a rotary evaporator to obtain a solid powder, and after the solid is dried, obtain the intermediate cI.

[0067] Step 2:

[0068] Add intermediate cI (1.0 eq) to a three-necked flask, add dichloromethane and stir until fully dissolved, cool to -10 to -20°C, add triethylsilane (0.05-0.07 eq), stir for 30-60 min, add trifluoromethanesulfonic acid (TfOH) (0.04-0.06 eq), warm to room temperature and stir overnight, add water to terminate the reaction, separate the liquids, collect the organic phase, extract the aqueous phase with dichloromethane three times, combine the organic phases, add anhydrous sodium sulfate to dry, remove the solvent by a rotary evaporator to obtain a solid powder, and after the solid is dried, obtain intermediate dI.

[0069] Step 3:

[0070] The intermediate dI (1.1-1.2 eq) was added to the reaction vessel, tetrahydrofuran was added and stirred until fully dissolved, potassium tert-butoxide (2.0-2.4 eq) was added and stirred for 2-3 h, the reactant eI (5.0-6 eq) was slowly added dropwise, refluxed and stirred overnight, cooled to room temperature, saturated ammonium chloride solution was added to quench the reaction, the liquids were separated, the organic phase was collected, the aqueous phase was extracted 3 times with dichloromethane, the organic phases were combined, anhydrous sodium sulfate was added to dry, the solvent was removed by a rotary evaporator to obtain a solid powder, and after the solid was dried, the intermediate fI was obtained.

[0071] Step 4:

[0072] Under N2 protection, add intermediate fI (1.0 eq) and reactant gI (1.1-1.4 eq) to a reaction vessel and dissolve in toluene, then add Pd2(dba)3 (0.01-0.02 eq), P(t-Bu)3 (0.05-0.1 eq), and t-BuONa (2.0-2.4 eq). After addition, heat to 105-115°C and react for 6-10 hours. Use diatomaceous earth to filter while hot to remove salt and catalyst. After the filtrate is cooled to room temperature, use a rotary evaporator to remove the solvent. After the solid is dried, pass through a silica gel funnel, use dichloromethane: petroleum ether volume ratio of 1: (1-4) as the eluent, remove the filtrate with a rotary evaporator, and dry the solid to obtain general formula I.

[0073] The present application also provides a light-emitting device, which 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, a capping layer, etc. as organic layers. However, the structure of the light-emitting device is not limited thereto, and may include fewer or more organic layers.

[0074] 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 general formula I prepared in the present application.

[0075] When manufacturing a light-emitting device, the compound represented by the general formula I may be formed into an organic layer by vacuum evaporation or solution coating, wherein the solution coating method refers to spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying, roller coating, etc., but is not limited thereto.

[0076] The light emitting device of the present application may be a top emission type, a bottom emission type or a bidirectional emission type according to the materials used.

[0077] The present application also provides a light-emitting device, which includes the light-emitting device mentioned above.

[0078] Specifically, the light-emitting device can be applied to an organic light-emitting device (OLED), an organic solar cell (OSC), electronic paper (e-paper), an organic photoreceptor (OPC) or an organic thin film transistor (OTFT), etc.

[0079] As the anode material, in order to enable holes to be smoothly injected into the organic layer, a material with a large work function is preferably used. Specific examples of the anode material that can be used in this application include metals such as vanadium, chromium, copper, zinc, gold, or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); combinations of metals and oxides such as ZnO: Al or SnO2: Sb; conductive polymers such as polypyrrole and polyaniline, etc.

[0080] The hole injection layer is preferably a P-doped hole injection layer, which means a hole injection layer doped with a P dopant. The P dopant is a material that can impart P-type semiconductor properties. The P-type semiconductor property means the property of injecting holes or transporting holes at the HOMO energy level, that is, the property of a material with high hole conductivity.

[0081] The P dopant for P doping may be exemplified by the following compounds, but is not limited thereto.

[0082]

[0083] The hole transport layer is placed between the anode and the light emitting layer, and it can be used to promote hole injection and / or hole transport, or to prevent electron overflow.

[0084] The hole transport layer material can be selected from aromatic amine derivatives, conductive polymers, and block copolymers having both conjugated and non-conjugated parts. Specifically, the hole transport layer material is selected from the following compounds, but is not limited thereto.

[0085]

[0086]

[0087] The compound represented by general formula I in the present application is used as a light-emitting auxiliary layer.

[0088] The light-emitting material of the light-emitting layer is a material that can receive holes and electrons from the hole transport layer and the electron transport layer, respectively, and combine them to emit light in the visible light region, and is preferably a material with high quantum efficiency for fluorescence or phosphorescence.

[0089] The light emitting layer may include a host material and a dopant material.

[0090] The mass ratio of the main material to the doping material is 90-99.5:0.5-10.

[0091] The main material includes aromatic fused ring derivatives or heterocyclic compounds, etc. Specifically, as aromatic fused ring derivatives, there are anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., as heterocyclic compounds, there are carbazole derivatives, dibenzofuran derivatives, pyrimidine derivatives, etc. Specifically, the main material of the present application is selected from the following compounds, but is not limited thereto.

[0092]

[0093]

[0094] The dopant materials of the present application include fluorescent doping and phosphorescent doping, and can be selected from aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, etc. Specifically, the doping materials of the present application are selected from the following compounds, but are not limited thereto.

[0095]

[0096]

[0097] The electron transport region may include at least one of an electron buffer layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and preferably at least one of an electron transport layer and an electron injection layer. The electron transport region is a layer that can improve the problem of degradation of luminous brightness due to changes in current characteristics in the device when the device is exposed to high temperature during the process of manufacturing the panel, and it can control charge flow characteristics.

[0098] Materials for the electron transport layer (hole blocking layer) include derivatives of oxazole, imidazole, thiazole, triazine, etc., metal chelates, quinoline derivatives, oxaline derivatives, diazanthracene derivatives, diazine derivatives, silicon-containing heterocyclic compounds, perfluorinated oligomers, etc. Specifically, the electron transport layer material is selected from the following compounds, but is not limited thereto.

[0099]

[0100]

[0101]

[0102] Materials for the electron injection layer include thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenyl methane, anthrone and their derivatives, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, ytterbium and other metals or their alloys, metal complexes or nitrogen-containing five-membered ring derivatives, etc., but are not limited to these.

[0103] The cathode material is usually preferably a material with a small work function in order to facilitate electron injection into the organic layer. Specific examples of cathode materials include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or their alloys: multilayer structures such as LiF / Al or LiO2 / Al, and Mg / Ag.

[0104] Except for the compound shown in Formula I in the light-emitting auxiliary layer disclosed in the present application, there is no special limitation on the materials of other layers in the OLED device. Existing hole injection materials, hole transport materials, dopant materials, hole blocking layer materials, electron transport layer materials and electron injection materials can be used.

[0105] The technical solutions in the embodiments of the present application are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.

[0106] In addition, it should be noted that the numerical values ​​given in the following examples are as accurate as possible, but those skilled in the art understand that due to unavoidable measurement errors and experimental operation problems, each number should be understood as an approximate number rather than an absolutely accurate value.

[0107] Example 1: Synthesis of Compound 2

[0108]

[0109] Step 1:

[0110] Reactant B-2 (55 mmol) was added to the reaction vessel, THF (300 mL) was added and stirred until fully dissolved, nitrogen was replaced three times, the temperature was lowered to -78°C, n-BuLi (55 mmol) was added dropwise, and the mixture was stirred at -78°C for 2 h. Reactant A-2 (50 mmol) was dissolved in tetrahydrofuran and added dropwise to the reaction system. After the addition was complete, the temperature was raised to room temperature and stirred for 8 h. Dilute hydrochloric acid was slowly added to terminate the reaction, the liquids were separated, the organic phase was collected, the aqueous phase was extracted 3 times with dichloromethane, the organic phases were combined, anhydrous sodium sulfate was added for drying, the solvent was removed by a rotary evaporator to obtain a solid powder, and after the solid was dried, intermediate C-2 (13.60 g, yield: 88%, Mw: 309.07) was obtained.

[0111] Step 2:

[0112] Under N2 protection, intermediate C-2 (40 mmol) was added to the reaction vessel, dissolved in HOAC (200 mL), heated to 100°C, H2SO4 (4 mL) was added dropwise, stirred for 1 h, cooled to room temperature, saturated sodium bicarbonate solution was added to terminate the reaction, the liquids were separated, the aqueous phase was extracted with dichloromethane, the organic phase was collected, anhydrous magnesium sulfate was added to dry, the solvent was removed by a rotary evaporator, and the solid was dried to obtain intermediate D-2 (10.47 g, yield: 90%, Mw: 290.94).

[0113] Step 3

[0114] Under N2 protection, add intermediate D-2 (34 mmol) and reactant E-2 (40.8 mmol) to the reaction vessel and dissolve in toluene, then add Pd2(dba)3 (0.34 mmol), P(t-Bu)3 (1.7 mmol), t-BuONa (68 mmol). After addition, heat to 105°C and react for 8 hours. Use diatomaceous earth to filter while hot to remove salt and catalyst. After the filtrate is cooled to room temperature, use a rotary evaporator to remove the solvent. After drying, the obtained solid is passed through a silica gel funnel, and dichloromethane: petroleum ether is used as an eluent in a volume ratio of 1:3. The filtrate is removed by a rotary evaporator, and the obtained solid is dried to obtain compound 2 (19.25 g, yield: 85%).

[0115] Characterization:

[0116] HPLC purity: >99.7%.

[0117] Mass spectrometry test: theoretical value is 665.88; test value is 666.11

[0118] Elemental Analysis:

[0119] Theoretical values: C, 91.99; H, 5.90; N, 2.10

[0120] Test values: C, 91.64; H, 6.24; N, 2.21

[0121] H NMR spectrum: Figure 1 shown.

[0122] Example 2: Synthesis of Compound 26

[0123]

[0124] Step 1:

[0125] Add reactant B-26 (55 mmol) to the reaction vessel, add THF (300 mL) and stir until fully dissolved, replace with nitrogen three times, cool to -78°C, add n-BuLi (55 mmol) dropwise, stir at -78°C for 2 h, dissolve reactant A-26 (50 mmol) in tetrahydrofuran and add dropwise to the reaction system. After the addition is complete, warm to room temperature and stir for 10 h; slowly add dilute hydrochloric acid to terminate the reaction, separate the liquids, collect the organic phase, extract the aqueous phase with dichloromethane three times, combine the organic phases, add anhydrous sodium sulfate to dry, remove the solvent by rotary evaporator to obtain a solid powder, and after the solid is dried, obtain intermediate C-26 (13.89 g, yield: 86%, Mw: 323.02).

[0126] Step 2:

[0127] Under N2 protection, intermediate C-26 (40 mmol) was added to the reaction vessel, dissolved in HOAC (200 mL), heated to 100°C, H2SO4 (4 mL) was added dropwise, stirred for 1 h, cooled to room temperature, saturated sodium bicarbonate solution was added to terminate the reaction, the liquids were separated, the aqueous phase was extracted with dichloromethane, the organic phase was collected, anhydrous magnesium sulfate was added to dry, the solvent was removed by a rotary evaporator, and the solid was dried to obtain intermediate D-26 (10.86 g, yield: 89%, Mw: 305.02).

[0128] Step 3

[0129] Under N2 protection, add intermediate D-26 (34 mmol) and reactant E-26 (40.8 mmol) to the reaction vessel and dissolve in toluene, then add Pd2(dba)3 (0.34 mmol), P(t-Bu)3 (1.7 mmol), t-BuONa (68 mmol). After addition, heat to 105°C and react for 8 hours. Use diatomaceous earth to filter while hot to remove salt and catalyst. After the filtrate is cooled to room temperature, use a rotary evaporator to remove the solvent. After drying, the obtained solid is passed through a silica gel funnel, and dichloromethane: petroleum ether volume ratio of 1:4 is used as the eluent. The filtrate is removed by a rotary evaporator, and the obtained solid is dried to obtain compound 26 (19.35 g, yield: 82%).

[0130] Characterization:

[0131] HPLC purity: >99.8%.

[0132] Mass spectrometry test: theoretical value is 693.89; test value is 694.13

[0133] Elemental Analysis:

[0134] Theoretical values: C, 90.01; H, 5.67; N, 2.02; O, 2.31

[0135] Found: C, 89.80; H, 5.81; N, 2.11; O, 2.40.

[0136] Example 3: Synthesis of Compound 46

[0137]

[0138] Step 1:

[0139] Add reactant B-46 (55 mmol) to the reaction vessel, add THF (300 mL) and stir until fully dissolved, replace with nitrogen three times, cool to -78°C, add n-BuLi (55 mmol) dropwise, stir at -78°C for 2 h, dissolve reactant A-46 (50 mmol) in tetrahydrofuran and add dropwise to the reaction system. After the addition is complete, warm to room temperature and stir for 8 h; slowly add dilute hydrochloric acid to terminate the reaction, separate the liquids, collect the organic phase, extract the aqueous phase with dichloromethane three times, combine the organic phases, add anhydrous sodium sulfate to dry, remove the solvent by rotary evaporator to obtain a solid powder, and after the solid is dried, obtain intermediate C-46 (15.10 g, yield: 86%, Mw: 351.21).

[0140] Step 2:

[0141] Under N2 protection, intermediate C-46 (40 mmol) was added to the reaction vessel, dissolved in HOAC (200 mL), heated to 100°C, H2SO4 (4 mL) was added dropwise, stirred for 1 h, cooled to room temperature, saturated sodium bicarbonate solution was added to terminate the reaction, the liquids were separated, the aqueous phase was extracted with dichloromethane, the organic phase was collected, anhydrous magnesium sulfate was added to dry, the solvent was removed by a rotary evaporator, and the solid was dried to obtain intermediate D-46 (11.99 g, yield: 90%, Mw: 333.18).

[0142] Step 3

[0143] Under N2 protection, add intermediate D-46 (34 mmol) and reactant E-46 (40.8 mmol) to the reaction vessel and dissolve in toluene, then add Pd2(dba)3 (0.34 mmol), P(t-Bu)3 (1.7 mmol), t-BuONa (68 mmol). After addition, heat to 105°C and react for 8 hours. Use diatomaceous earth to filter while hot to remove salt and catalyst. After the filtrate is cooled to room temperature, use a rotary evaporator to remove the solvent. After drying, the obtained solid is passed through a silica gel funnel, and dichloromethane: petroleum ether volume ratio of 1:2 is used as the eluent. The filtrate is removed by a rotary evaporator, and the obtained solid is dried to obtain compound 46 (18.74 g, yield: 84%).

[0144] Characterization:

[0145] HPLC purity: >99.7%.

[0146] Mass spectrometry test: Theoretical value is 655.84: Test value is 656.15

[0147] Elemental Analysis:

[0148] Theoretical values: C, 89.74; H, 5.69; N, 2.14; O, 2.44

[0149] Measured values: C, 89.47; H, 5.89; N, 2.22; O, 2.51

[0150] H NMR spectrum: Figure 2 shown.

[0151] Example 4: Synthesis of Compound 76

[0152]

[0153] Step 1:

[0154] Add reactant b-76 (55 mmol) to the reaction vessel, add THF and stir until fully dissolved, replace with nitrogen three times, cool to -78°C, add n-BuLi (60 mmol) dropwise, stir for 2 h, dissolve reactant a-76 (50 mmol) in tetrahydrofuran, add dropwise to the reaction system, after the addition is complete, warm to room temperature and stir for 10 h; slowly add dilute hydrochloric acid to terminate the reaction, separate the liquids, collect the organic phase, extract the aqueous phase with dichloromethane three times, combine the organic phases, add anhydrous sodium sulfate to dry, remove the solvent by rotary evaporator to obtain a solid powder, and after the solid is dried, obtain intermediate c-76 (17.52 g, yield: 88%, Mw: 398.23).

[0155] Step 2:

[0156] Add intermediate c-76 (43 mmol) to a three-necked flask in a reaction vessel, add dichloromethane and stir until fully dissolved, cool to -10°C, add triethylsilane (Triethylsilane) (2.15 mmol), stir for 30 min, add trifluoromethanesulfonic acid (TfOH) (2.15 mmol), warm to room temperature and stir overnight, add water to terminate the reaction, separate the liquids, collect the organic phase, extract the aqueous phase three times with dichloromethane, combine the organic phases, add anhydrous sodium sulfate to dry, remove the solvent by rotary evaporator to obtain a solid powder, and after the solid is dried, obtain intermediate d-76 (14.79 g, yield: 90%, Mw: 382.16).

[0157] Step 3:

[0158] Add intermediate d-76 (36 mmol) to the reaction vessel, add tetrahydrofuran and stir until fully dissolved, add potassium tert-butoxide (79.2 mmol) and stir for 2 h, slowly add reactant e-76 (180 mmol) dropwise, reflux with stirring overnight, cool to room temperature, add saturated ammonium chloride solution to quench the reaction, separate the liquids, collect the organic phase, extract the aqueous phase with dichloromethane 3 times, combine the organic phases, add anhydrous sodium sulfate to dry, remove the solvent by rotary evaporator to obtain a solid powder, and after the solid is dried, obtain intermediate f-76 (12.41 g, yield: 87%, Mw: 396.25).

[0159] Step 4:

[0160] Under N2 protection, add intermediate f-76 (31mmol) and reactant g-76 (34.1mmol) to the reaction vessel and dissolve in toluene, then add Pd2(dba)3 (0.31mmol), P(t-Bu)3 (1.55mmol), t-BuONa (68.2mmol). After addition, heat to 110°C and react for 8h. Use diatomaceous earth to filter while hot to remove salt and catalyst. After the filtrate is cooled to room temperature, use a rotary evaporator to remove the solvent. After drying, the obtained solid is passed through a silica gel funnel, and dichloromethane: petroleum ether volume ratio of 1:3 is used as the eluent. The filtrate is removed by a rotary evaporator, and the obtained solid is dried to obtain compound 76 (17.45g, yield: 81%).

[0161] Characterization:

[0162] HPLC purity: >99.7%.

[0163] Mass spectrometry test: theoretical value is 694.92; test value is 695.03

[0164] Elemental Analysis:

[0165] Theoretical values: C, 89.88; H, 6.09; N, 4.03

[0166] Test values: C, 89.70; H, 6.30; N, 4.11

[0167] H NMR spectrum: Figure 3 shown.

[0168] Example 5: Synthesis of Compound 117

[0169]

[0170] Step 1:

[0171] Add reactant b-117 (55 mmol) to the reaction vessel, add THF and stir until fully dissolved, replace with nitrogen three times, cool to -78°C, add n-BuLi (60 mmol) dropwise, stir for 2 h, dissolve reactant a-117 (50 mmol) in tetrahydrofuran, add dropwise to the reaction system, after the addition is complete, warm to room temperature and stir for 10 h; slowly add dilute hydrochloric acid to terminate the reaction, separate the liquids, collect the organic phase, extract the aqueous phase with dichloromethane 3 times, combine the organic phases, add anhydrous sodium sulfate to dry, remove the solvent by rotary evaporator to obtain a solid powder, and after the solid is dried, obtain intermediate c-117 (17.72 g, yield: 86%, Mw: 412.22).

[0172] Step 2:

[0173] Add intermediate c-117 (43 mmol) into a three-necked flask, add dichloromethane and stir until fully dissolved, cool to -10°C, add triethylsilane (Triethylsilane) (2.15 mmol), stir for 30 min, add trifluoromethanesulfonic acid (TfOH) (2.15 mmol), warm to room temperature and stir overnight, add water to terminate the reaction, separate the liquids, collect the organic phase, extract the aqueous phase three times with dichloromethane, combine the organic phases, add anhydrous sodium sulfate to dry, remove the solvent by rotary evaporator to obtain a solid powder, and after the solid is dried, obtain intermediate d-117 (14.31 g, yield: 84%, Mw: 396.08).

[0174] Step 3:

[0175] Add intermediate d-117 (36 mmol) to the reaction vessel, add tetrahydrofuran and stir until fully dissolved, add potassium tert-butoxide (79.2 mmol) and stir for 2 h, slowly add reactant e-117 (180 mmol) dropwise, reflux with stirring overnight, cool to room temperature, add saturated ammonium chloride solution to quench the reaction, separate the liquids, collect the organic phase, extract the aqueous phase with dichloromethane 3 times, combine the organic phases, add anhydrous sodium sulfate to dry, remove the solvent by rotary evaporator to obtain a solid powder, and after the solid is dried, obtain intermediate f-117 (11.44 g, yield: 88%, Mw: 361.08).

[0176] Step 4:

[0177] Under N2 protection, add intermediate f-117 (31 mmol) and reactant g-117 (34.1 mmol) to the reaction vessel and dissolve in toluene, then add Pd2(dba)3 (0.31 mmol), P(t-Bu)3 (1.55 mmol), t-BuONa (68.2 mmol). After addition, heat to 110°C and react for 8 hours. Use diatomaceous earth to filter while hot to remove salt and catalyst. After the filtrate is cooled to room temperature, use a rotary evaporator to remove the solvent. After drying the solid, pass it through a silica gel funnel, use dichloromethane: petroleum ether volume ratio of 1:3 as eluent, remove the filtrate with a rotary evaporator, dry the solid, and obtain compound 117 (20.23 g, yield: 83%).

[0178] Characterization:

[0179] HPLC purity: >99.8%.

[0180] Mass spectrometry test: theoretical value is 786.08; test value is 786.30

[0181] Elemental Analysis:

[0182] Theoretical values: C, 91.68; H, 6.54; N, 1.78

[0183] Measured values: C, 91.54; H, 6.71; N, 1.82.

[0184] Example 6-Example 46

[0185] The synthesis of compounds 1, 3, 4, 6, 7, 8, 11, 12, 13, 15, 16, 17, 19, 20, 22, 24, 27, 28, 31, 32, 35, 39, 40, 44, 48, 51, 53, 57, 64, 67, 72, 73, 75, 80, 85, 91, 95, 104, 111, 124, 129 was completed by referring to the synthesis method of Examples 1 to 5. The corresponding mass spectra and molecular formulas are shown in Table 1 below.

[0186] Table 1

[0187]

[0188]

[0189] In addition, it should be noted that other compounds of the present application can be obtained by referring to the synthesis methods of the above-listed embodiments, so they will not be listed one by one here.

[0190] Application Example 1 Preparation of red light organic electroluminescent device:

[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 HT1-7 and P-9 are vacuum evaporated at a deposition rate of 97:3, and the thickness is 10 nm;

[0193] c. HTL (hole transport layer): At a deposition rate of 100%, 125 nm of HT1-7 was vacuum-deposited on the hole injection layer as a hole transport layer.

[0194] d. Light-emitting auxiliary layer: At a deposition rate of , 100 nm of the compound 1 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 main material Host-15 and the dopant material Dopant-R-1 are vacuum-deposited at a thickness of 40 nm as the light-emitting layer, wherein the evaporation rate ratio of Host-15 to Dopant-R-1 is 97:3.

[0196] f. HB (hole blocking layer): The evaporation rate was 5.0 nm, and HB was vacuum evaporated to a thickness of 5.0 nm as a hole blocking layer.

[0197] g. ETL (Electron Transport Layer): ET-10 and Liq were vacuum-deposited at a deposition rate of 30 nm as an electron transport layer, wherein the deposition rate ratio of ET-10 to Liq was 50:50.

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

[0199] i. Cathode: The evaporation rate ratio is 1:9, and magnesium and silver are evaporated 18nm, and the evaporation rate ratio is 1:9 to form a cathode.

[0200] j. Light extraction layer: At a deposition rate of , CPL 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] Red light device structure: ITO / Ag / ITO / HT1-7:P-9(10nm) / HT1-7(125nm) / Compound 1(100nm) / Host-15:Dopant-R-1(40nm) / HB(5nm) / ET-10:Liq(30nm) / Yb(1nm) / Mg:Ag(18nm) / CPL(70nm).

[0203] The materials required for each layer are as follows:

[0204]

[0205]

[0206] Application Example 2-33

[0207] The organic electroluminescent devices of Application Examples 2-33 were prepared according to the above-mentioned method for preparing an organic electroluminescent device, except that the compound 1 in Application Example 1 was replaced by corresponding compounds to form a light-emitting auxiliary layer.

[0208] Comparative Example 1

[0209] An organic electroluminescent device was prepared according to the above-mentioned method for preparing an organic electroluminescent device, except that the compound 1 in Application Example 1 was replaced by a comparative compound 1, wherein the structural formula of the comparative compound 1 is as follows:

[0210] Comparative Example 2

[0211] An organic electroluminescent device was prepared according to the above-mentioned method for preparing an organic electroluminescent device, except that the compound 1 in Application Example 1 was replaced by a comparative compound 2, wherein the structural formula of the comparative compound 2 is as follows:

[0212] Comparative Example 3

[0213] An organic electroluminescent device was prepared according to the above-mentioned method for preparing an organic electroluminescent device, except that the compound 1 in Application Example 1 was replaced by a comparative compound 3, wherein the structural formula of the comparative compound 3 is as follows:

[0214] Comparative Example 4

[0215] An organic electroluminescent device was prepared according to the above-mentioned method for preparing an organic electroluminescent device, except that the compound 1 in Application Example 1 was replaced by a comparative compound 4, wherein the structural formula of the comparative compound 4 is as follows:

[0216]

[0217] The driving voltage, luminous efficiency, and life of the organic electroluminescent devices obtained from the device embodiments 1-33 and the device comparative examples 1-4 were characterized at a brightness of 6000 (nits). The test results are shown in Table 2 below:

[0218] Table 2 Luminous characteristics test results (brightness value is 6000nits)

[0219]

[0220]

[0221] Application Example 34 Preparation of green organic electroluminescent device:

[0222] 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.

[0223] b. HIL (hole injection layer): The hole injection layer materials HT1-9 and P-9 are vacuum evaporated at a deposition rate of 97:3, and the thickness is 10 nm;

[0224] c. HTL (hole transport layer): At a deposition rate of 100%, 120 nm of HT1-9 was vacuum-deposited on the hole injection layer as a hole transport layer.

[0225] d. Light-emitting auxiliary layer: At a deposition rate of , 45 nm of the compound 2 provided in the above embodiment is vacuum-deposited on the hole transport layer as a light-emitting auxiliary layer;

[0226] e. EML (light-emitting layer): Then on the above-mentioned light-emitting auxiliary layer, The evaporation rate of the main material (Host-22 and Host-23) and the dopant material (Dopant-G-16) with a thickness of 400nm were vacuum evaporated as the light-emitting layer, wherein Host-22 and Host-23 were co-evaporated as dual main materials with the dopant material, and the ratio of Host-22 to Host-23 was 50%:50%. The chemical formulas of Host-22, Host-23 and Dopant are shown below. The evaporation rate ratio of the main material and Dopant was 88:12.

[0227] f. HBL (hole blocking layer): The hole blocking layer HB with a thickness of 5.0 nm was vacuum deposited at a deposition rate of .

[0228] g. ETL (Electron Transport Layer): ET-8 and Liq were vacuum-deposited at a deposition rate of 30 nm as the electron transport layer, where the deposition rate ratio of ET-8 to Liq was 50:50.

[0229] h. EIL (electron injection layer): The evaporation rate is 1.0 nm, and a Yb film layer is evaporated to form an electron injection layer.

[0230] i. Cathode: The evaporation rate ratio is 1:9, and magnesium and silver are evaporated 18nm, and the evaporation rate ratio is 1:9 to form a cathode.

[0231] j. Light extraction layer: At a deposition rate of , CPL with a thickness of 70 nm was vacuum-deposited on the cathode as a light extraction layer.

[0232] 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.

[0233] Green light device structure: ITO / Ag / ITO / HT1-9:P-9(10nm) / HT1-9(120nm) / Compound 2(45nm) / (Host-22+Host-23):Dopant-G-16(400nm) / HB(5nm) / ET-8:Liq(30nm) / Yb(1n m) / Mg:Ag(18nm) / CPL(70nm).

[0234]

[0235] Application Examples 35-57

[0236] The organic electroluminescent devices of Application Examples 35-57 are prepared according to the preparation method of the organic electroluminescent device Application Example 34, except that the compound 2 in Application Example 34 is replaced by the corresponding compound to form a light-emitting auxiliary layer.

[0237] The driving voltage, luminous efficiency, and life of the organic electroluminescent devices obtained from the device embodiments 34-57 and the device comparative examples 5-8 were characterized at a brightness of 15000 (nits). The test results are shown in Table 3 below:

[0238] Comparative Examples 5-8

[0239] An organic electroluminescent device is prepared according to the above-mentioned method for preparing an organic electroluminescent device, except that the compound 2 in Application Example 34 is replaced by comparative compound 1-4, wherein the structural formula of comparative compound 1-4 is shown above.

[0240] Table 3 Luminous characteristics test results (brightness value is 15000nits)

[0241]

[0242] It can be seen from Table 2 and Table 3 that, compared with the existing organic electroluminescent devices provided in Comparative Examples 1-8, the organic electroluminescent device application examples 1-57 prepared using the luminescent auxiliary layer material provided in the present application are used in red and green light devices, and the driving voltage is reduced, and the luminescent efficiency and life are improved, and the luminescent auxiliary layer material provided in the present application can be applied to both red and green light organic electroluminescent devices.

[0243] Comparative compound 1 and compound 39 are compared in parallel, and comparative compound 2 is compared in parallel with compound 11 and compound 22. The difference is that the substitution positions of the substituents are different, which can improve the device performance of the compounds.

[0244] The comparison of compound 3 with compound 2 and compound 17 is parallel, and it can be seen that the benzene ring on dibenzofuran / fluorene improves the efficiency, life span and driving voltage performance of the compound.

[0245] For the red light hosts used in this application, significant progress has been made in terms of 3-5% improvement in efficiency and 4-8% improvement in efficiency for the green light hosts.

[0246] In this specification, each embodiment is described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the embodiments can be referred to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant parts can be referred to the method part.

[0247] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present application. Various modifications to these embodiments will be apparent to those 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 application. Therefore, the present application will not be limited to the embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A light-emitting auxiliary layer material, characterized in that: The structure of the light-emitting auxiliary layer material is shown in Formula I: Wherein in the general formula I, n is an integer selected from 1, 2, 3, 4; R1 is arbitrarily substituted on the benzene ring; R1 is one of hydrogen, methyl, ethyl, propyl, isopropyl, and tert-butyl; R2 is one of methyl, ethyl, propyl and isopropyl; Ring A is a phenyl group fused to an adjacent benzene ring; X is one of O, S, -C(CH3)2-; Y is a single bond, one of O, S, -CR3R4-, and -NR5-; R3-R4 are each independently selected from methyl, ethyl, propyl, phenyl, naphthyl, phenanthryl, biphenyl, terphenyl, methylphenyl, pyridyl, phenylpyridyl; R5 is independently selected from phenyl, naphthyl, methylphenyl, biphenyl, dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl; Ar1 is independently selected from the following groups:

2. The light-emitting auxiliary layer material according to claim 1, characterized in that: The light-emitting auxiliary layer material is one of the following compounds:

3. The light-emitting auxiliary layer material according to claim 1, characterized in that: The n is selected from 1 and 2; the X is selected from O and -C(CH3)2-.

4. The light-emitting auxiliary layer material according to claim 1, characterized in that: The light-emitting auxiliary layer material is one of the following compounds:

5. The light-emitting auxiliary layer material according to claim 1, characterized in that: The light-emitting auxiliary layer material is one of the following compounds:

6. A light emitting device, characterized in that: The light-emitting device comprises the light-emitting auxiliary layer material according to any one of claims 1 to 5.

7. A light emitting device, characterized in that: The light-emitting device comprises the light-emitting auxiliary layer material according to any one of claims 1 to 5 or the light-emitting device according to claim 6.

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