A light-emitting auxiliary material and preparation method thereof, and a light-emitting device

Abstract

The present application is applicable to the field of material technology, and provides a luminescent auxiliary material and a preparation method thereof, and a luminescent device. The present application uses characteristic compounds as luminescent auxiliary materials of organic electroluminescent devices by limiting the type of linking base connected to the core, the type of amine group bonded to the linking base, and the bonding position, thereby greatly improving the hole transport efficiency and electron blocking ability, and increasing the charge balance of holes and electrons in the luminescent layer, so that luminescence is well formed inside the luminescent layer instead of on the surface of the hole transport layer, thereby improving the luminescence efficiency and life of the organic electroluminescent device by easily achieving charge balanced HOMO energy levels in the luminescent layer.

Description

Technical Field

[0001] The present application belongs to the field of material technology, and in particular relates to a luminescent auxiliary material and a preparation method thereof, and a luminescent device. Background Art

[0002] Generally speaking, the organic light-emitting phenomenon refers to the phenomenon of converting electrical energy into light energy using organic substances. Organic light-emitting devices using the organic light-emitting phenomenon have wide viewing angles, excellent contrast, fast response time, excellent brightness, driving voltage and response speed characteristics, so a lot of research is being carried out. Many improvements have been made to make organic EL devices practically applicable. For example, it is well known that high efficiency and high durability can be achieved by further allocating the various effects of the laminated structure and forming an anode, and a hole injection layer, a hole transport layer, a hole blocking layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode are arranged on the substrate. With this organic EL device, the charges injected from the two electrodes are recombined in the light-emitting layer to obtain light emission. In this case, how to effectively transfer the charges of holes and electrons to the light-emitting layer is important, and the device needs to have excellent carrier balance. Moreover, by enhancing the hole injection characteristics and electron blocking characteristics of blocking the electrons injected from the cathode to increase the recombination probability of holes and electrons, and by limiting the excitons generated in the light-emitting layer, the luminous efficiency is improved. Therefore, the role of the light-emitting auxiliary material is so important.

[0003] Research on organic electroluminescent materials has been widely carried out in academia and industry, but so far, stable and efficient organic layer materials for organic electrical components have not been fully developed, and the industrialization process of this technology still faces many key problems. Therefore, the development of new materials has always been an urgent problem to be solved by technical personnel in this field. Summary of the invention

[0004] The purpose of the present application is to provide a luminescent auxiliary material, aiming to solve the problem that the luminescent efficiency and life of existing organic electroluminescent devices are not significantly improved.

[0005] The present application is implemented as follows: a luminescence auxiliary material, the general structural formula of the luminescence auxiliary material is shown in Chemical Formula I:

[0006]

[0007] X is selected from one of O and S; Y is selected from a connecting bond, C(R 6 ,R 7 ), O, S, NR 8 One of;

[0008] R 1independently represents one of hydrogen, deuterium, halogen, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted 3-20 membered heterocycloalkyl, wherein the heteroatom is N, O, S, Si, P, Se;

[0009] R 2 , R 3 independently represents hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic acid, phosphoric acid, borane, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C20 cycloalkyl except adamantyl, substituted or unsubstituted 3-20 membered heterocycloalkyl, wherein the heteroatom is N, O, S, Si, P, Se, etc.; substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-30 membered heteroaryl, wherein the heteroatom is N, O, S, Si, P, Se; wherein R 2 , R 3 They cannot be connected to form a ring;

[0010] R 4 , R 5 independently represents hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic acid, phosphoric acid, borane, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted 3-20 membered heterocycloalkyl, wherein the heteroatom is N, O, S, Si, P, Se; substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-30 membered heteroaryl, wherein the heteroatom is N, O, S, Si, P, Se;

[0011] R 6 , R 7 , R 8 independently represents hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted 3-20 membered heterocycloalkyl, wherein the heteroatom is N, O, S, Si, P, Se, etc.; substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-30 membered heteroaryl, wherein the heteroatom is N, O, S, Si, P, Se;

[0012] Ar is a substituent fused to the benzene ring, and Ar may be fused to the 12-position or 34-position of the benzene ring.

[0013] Ar represents a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted 3-20-membered heteroaryl group, wherein the heteroatom is selected from O, N, and S;

[0014] Ar 1independently represents a substituted or unsubstituted C3-C30 cycloalkyl, a substituted or unsubstituted 3- to 30-membered heterocycloalkyl, wherein the heteroatom is N, O, S, Si, P, or Se; a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted 3- to 30-membered heteroaryl, wherein the heteroatom is N, O, S, Si, P, or Se; or a substituted or unsubstituted C10-C30 fused ring group;

[0015] Ar 2 Independently represented as diphenylamine group.

[0016] Another object of the present application is a method for preparing a luminescent auxiliary material, comprising:

[0017]

[0018] The raw materials A and B are dissolved in a toluene solution, tri(dibenzylideneacetone)dipalladium, tri-tert-butylphosphine and sodium tert-butoxide are added under nitrogen protection, stirred evenly, and heated to reflux for reaction to obtain intermediate 1;

[0019] The intermediate 1 and the raw material C are dissolved in a toluene solution, tri(dibenzylideneacetone)dipalladium, tri-tert-butylphosphine and sodium tert-butoxide are added under nitrogen protection, stirred evenly, and heated to reflux for reaction to obtain the intermediate 2;

[0020] The intermediate 2 and the raw material D are dissolved in a toluene solution, tri(dibenzylideneacetone)dipalladium, tri-tert-butylphosphine and sodium tert-butoxide are added under nitrogen protection, stirred evenly, and heated to reflux for reaction to obtain the luminescent auxiliary material shown in chemical formula I.

[0021] Another object of the present application is a light-emitting device, which includes the light-emitting auxiliary material or the light-emitting auxiliary material prepared according to the preparation method of the light-emitting auxiliary material.

[0022] The luminescence auxiliary material provided in the present application, by limiting the type of linking group connected to the core, the type of amine group bonded to the linking group, and the characteristic compound of the bonding position, is used as a luminescence auxiliary material of an organic electroluminescent device, which greatly improves the hole transport efficiency and the electron blocking ability, and increases the charge balance of holes and electrons in the luminescent layer, so that luminescence is well formed inside the luminescent layer instead of on the surface of the hole transport layer, thereby improving the luminescence efficiency and life of the organic electroluminescent device by easily achieving a charge balanced HOMO energy level in the luminescent layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is the hydrogen nuclear magnetic resonance spectrum of compound 9 provided in Example 1 of the present application;

[0024] Figure 2is the hydrogen nuclear magnetic resonance spectrum of compound 83 provided in Example 2 of the present application;

[0025] Figure 3 is the hydrogen nuclear magnetic resonance spectrum of compound 119 provided in Example 3 of the present application;

[0026] Figure 4 This is the hydrogen nuclear magnetic resonance spectrum of compound 238 provided in Example 4 of the present application. DETAILED DESCRIPTION

[0027] 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.

[0028] The present application provides a luminescent auxiliary material, the general structural formula of which is shown in Chemical Formula I:

[0029]

[0030] In the chemical formula I:

[0031] X is selected from O, S; Y is selected from a linker, C(R6, R7), O, S, NR8;

[0032] R 1 independently represents hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C25) alkyl, substituted or unsubstituted (C3-C20) cycloalkyl, substituted or unsubstituted (3-20-membered) heterocycloalkyl, wherein the heteroatom is N, O, S, Si, P, Se, etc.;

[0033] R 2 , R 3 independently represents hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic acid, phosphoric acid, borane, substituted or unsubstituted (C1-C25) alkyl, substituted or unsubstituted (C3-C20) cycloalkyl (except adamantyl), substituted or unsubstituted (3-20-membered) heterocycloalkyl, wherein the heteroatom is N, O, S, Si, P, Se, etc.; substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-30-membered) heteroaryl, wherein the heteroatom is N, O, S, Si, P, Se, etc.; wherein R 2 , R 3 They cannot be connected to form a ring.

[0034] R 4 , R 5independently represents hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic acid, phosphoric acid, borane, substituted or unsubstituted (C1-C25) alkyl, substituted or unsubstituted (C3-C20) cycloalkyl, substituted or unsubstituted (3-20-membered) heterocycloalkyl, wherein the heteroatom is N, O, S, Si, P, Se, etc.; substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-30-membered) heteroaryl, wherein the heteroatom is N, O, S, Si, P, Se, etc.;

[0035] R 6 , R 7 , R 8 independently represents hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C20) alkyl, substituted or unsubstituted (C3-C20) cycloalkyl, substituted or unsubstituted (3-20-membered) heterocycloalkyl, wherein the heteroatom is N, O, S, Si, P, Se, etc.; substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-30-membered) heteroaryl, wherein the heteroatom is N, O, S, Si, P, Se, etc.;

[0036] Ar is a substituent fused to the benzene ring, and Ar may be fused to the 12-position or 34-position of the benzene ring.

[0037] Ar represents a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted (3-20-membered) heteroaryl group, wherein the heteroatom thereof is selected from oxygen (O), nitrogen (N) and sulfur (S);

[0038] Ar 1 independently represents substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (3- to 30-membered) heterocycloalkyl, wherein the heteroatom is N, O, S, Si, P, Se, etc.; substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3- to 30-membered) heteroaryl, wherein the heteroatom is N, O, S, Si, P, Se, etc.; substituted or unsubstituted (C10-C30) fused ring group;

[0039] Ar 2 Independently represented as diphenylamine group;

[0040] The preferred general structural formula of the above chemical formula I is:

[0041]

[0042] Wherein X, Y, R1 to R5, Ar1 and Ar2 in the above Chemical Formula-Ia to Chemical Formula-Ib are as defined above.

[0043] Further preferably, Y is selected from a connecting bond;

[0044] More preferably, R 2 , R 3 represents hydrogen;

[0045] More preferably, Ar represents a substituted or unsubstituted (C6-C20) aryl group, a substituted or unsubstituted (3-20-membered) heteroaryl group, wherein the heteroatom is N, O, S, Si, P, Se, etc.;

[0046] More preferably, Ar is phenyl;

[0047] More preferably, Ar 1 express:

[0048]

[0049] The above chemical formula I has a further preferred general structural formula:

[0050]

[0051]

[0052] In the above technical scheme, the term "substituted or unsubstituted" means substituted by one, two or more substituents selected from the following: hydrogen; deuterium; halogen group; nitrile group; C1-C5 alkyl; C6-C20 aryl; C6-C18 heteroaryl; or substituted by two or more substituents connected to each other among the substituents shown above, or having no substituents. For example, "a substituent in which two or more substituents are connected to each other" may include a biphenyl group. In other words, the biphenyl group may be an aryl group, or may be interpreted as a substituent in which two phenyl groups are connected to each other.

[0053] In the above technical solution, it is further preferred that the light-emitting auxiliary material is any one of the following structures, but not limited thereto:

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063] Another object of the present application is to provide a method for preparing the above-mentioned luminescence auxiliary material, preferably prepared by the following reaction process.

[0064] Synthetic route 1:

[0065]

[0066] Step 1, preparation of intermediate 1

[0067] The raw material A (1.0 eq) and the raw material B (1.0 eq) were dissolved in a toluene solution, and then ventilated 3 times. Tri(dibenzylideneacetone)dipalladium (0.01 eq), tri-tert-butylphosphine (0.05 eq) and sodium tert-butoxide (2.0 eq) were added under nitrogen protection, stirred evenly, heated to reflux, and reacted for 5 h. After the reaction was completed, the temperature was slightly lowered, and diatomaceous earth was used for filtering to remove salt and catalyst. After the filtrate was cooled to room temperature, it was washed with water three times, and the organic phase was retained. Then, the aqueous phase was extracted with ethyl acetate. After the organic phases were combined, they were dried with anhydrous magnesium sulfate, and the solvent was removed with a rotary evaporator. A small amount of dichloromethane was used to completely dissolve the solid organic matter, and then it was slowly added dropwise to the petroleum ether solution, stirred evenly, and a precipitate was precipitated. The solid was filtered to obtain the solid, and it was rinsed with 300 mL of anhydrous ethanol and 200 mL of petroleum ether in turn, and dried to obtain intermediate 1.

[0068] Step 2, preparation of intermediate 2

[0069] The intermediate 1 (1.0 eq) and the raw material C (1.0 eq) were dissolved in a toluene solution, and then ventilated 3 times. Tri(dibenzylideneacetone)dipalladium (0.01 eq), tri-tert-butylphosphine (0.05 eq) and sodium tert-butoxide (2.0 eq) were added under nitrogen protection, stirred evenly, heated to reflux, and reacted for 5 h. After the reaction was completed, the temperature was slightly lowered, and diatomaceous earth was used for filtering to remove salt and catalyst. After the filtrate was cooled to room temperature, it was washed three times with water, and the organic phase was retained. Then, the aqueous phase was extracted with ethyl acetate. After the organic phases were combined, they were dried with anhydrous magnesium sulfate, and the solvent was removed with a rotary evaporator. A small amount of dichloromethane was used to completely dissolve the solid organic matter, and then it was slowly added dropwise to the petroleum ether solution, stirred evenly, and a precipitate was precipitated. The solid was filtered to obtain the solid, and it was rinsed with 300 mL of anhydrous ethanol and 200 mL of petroleum ether in turn, and dried to obtain the intermediate 2.

[0070] Step 3, preparation of intermediate 3

[0071] The intermediate 2 (1.0 eq) and the raw material D (1.0 eq) were dissolved in a toluene solution, and then ventilated 3 times. Tri(dibenzylideneacetone)dipalladium (0.01 eq), tri-tert-butylphosphine (0.05 eq) and sodium tert-butoxide (2.0 eq) were added under nitrogen protection, stirred evenly, heated to reflux, and reacted for 5 h. After the reaction was completed, the temperature was slightly lowered, and diatomaceous earth was used for filtering to remove salt and catalyst. After the filtrate was cooled to room temperature, it was washed with water three times, the organic phase was retained, and then the aqueous phase was extracted with ethyl acetate. After the organic phases were combined, they were dried with anhydrous magnesium sulfate, and the solvent was removed with a rotary evaporator. The remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V dichloromethane: V petroleum ether = 10:4) to obtain Chemical Formula I.

[0072] Among them, X, Y, Ar, Ar 1 ,Ar 2 , R 1 ~R 5 As defined in Formula I above.

[0073] Another object of an embodiment of the present application is to provide a light-emitting device, comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode.

[0074] The organic material layer of the light-emitting device of the present disclosure may be formed as a single-layer structure, but may also be formed as a multilayer structure in which a layer and two or more organic material layers are formed. For example, the light-emitting device of the present disclosure may have a structure including a hole injection layer, a hole transport layer, a hole injection and transport layer, an electron blocking layer, a light-emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron injection and transport layer, etc. as organic material layers. However, the structure of the light-emitting device is not limited thereto, and may include a smaller number of organic material layers or a larger number of organic material layers.

[0075] As the anode material, a material with a large work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of anode materials that can be used in the present disclosure include: metals, such as vanadium, chromium, copper, zinc and gold, or alloys thereof; metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); combinations of metals and oxides, such as ZnO:Al or SnO2:Sb; conductive polymers, such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole and polyaniline, but are not limited thereto.

[0076] The hole injection material is a material that advantageously receives holes from the anode at a low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrins, oligothiophenes, organic materials based on arylamines, organic materials based on hexanitrile hexaazatriphenylene, organic materials based on quinacridone, organic materials based on perylene, anthraquinone, and conductive polymers based on polyaniline and polythiophene, etc., but are not limited thereto, and may also include additional compounds capable of p-doping.

[0077] The hole transport material is a material that can receive holes from the anode or the hole injection layer and transport the holes to the light-emitting layer, and a material having a high hole mobility is suitable. Specific examples thereof include organic materials based on arylamine, conductive polymers, block copolymers having both a conjugated portion and a non-conjugated portion, etc., but are not limited thereto.

[0078] The light-emitting layer can emit red, green or blue light, and can be formed of a phosphorescent material or a fluorescent material. The light-emitting material is a material that can emit light in the visible light region by receiving holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining the holes with the electrons, and is preferably a material with a favorable quantum efficiency for fluorescence or phosphorescence. Specific examples thereof include: 8-hydroxyquinoline aluminum (Alq3); carbazole-based compounds; diphenylethylene compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; benzocarbazole-based, benzothiazole-based and benzimidazole-based compounds; poly(p-phenylene vinylene) (PPV)-based polymers; spiro compounds; polyfluorene; rubrene, etc., but are not limited thereto.

[0079] The host material of the light-emitting layer includes fused aromatic ring derivatives, heterocyclic compounds, etc. Specifically, the fused aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and the heterocyclic compounds include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, etc., however, the materials are not limited thereto.

[0080] The electron transport layer can play a role in promoting electron transport. The electron transport material is a material that advantageously receives electrons from the cathode and transports the electrons to the light-emitting layer, and a material with high electron mobility is suitable. Specific examples thereof include: Al complexes of 8-hydroxyquinoline; complexes containing Alq3; organic free radical compounds; hydroxyflavone-metal complexes; and the like, but are not limited thereto. The thickness of the electron transport layer can be 1 nm to 50 nm. An electron transport layer with a thickness of 1 nm or more has the advantage of preventing the electron transport characteristics from decreasing, and a thickness of 50 nm or less has the advantage of preventing an increase in the driving voltage for enhancing electron migration caused by the electron transport layer being too thick.

[0081] The electron injection layer can play a role in promoting electron injection. The electron injection material is preferably a compound that has the ability to transport electrons, has an effect of injecting electrons from the cathode, has an excellent electron injection effect on the light-emitting layer or the light-emitting material, prevents the excitons generated in the light-emitting layer from migrating to the hole injection layer, and in addition, has excellent film forming ability. Specific examples thereof include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, azole, diazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenyl methane, anthrone, etc. and their derivatives, metal complexes, nitrogen-containing 5-membered ring derivatives, etc., but are not limited thereto.

[0082] As the cathode material, a material having a small work function is generally preferred so that electrons can be smoothly injected into the organic material 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 alloys thereof; multilayer structure materials such as LiF / Al or LiO2 / Al; etc., but are not limited thereto.

[0083] The light-emitting device provided in the present application 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).

[0084] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the luminescent auxiliary materials of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments.

[0085] 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.

[0086] Example 1

[0087]

[0088] The raw material A-9 (30.00 mmol) and the raw material B-9 (30.00 mmol) were dissolved in a toluene solution, and then ventilated 3 times. Tri(dibenzylideneacetone)dipalladium (0.30 mmol), tri-tert-butylphosphine (1.50 mmol) and sodium tert-butoxide (60.00 mmol) were added under nitrogen protection, stirred evenly, heated to 90°C, and refluxed for 5 hours. After the reaction was completed, the temperature was slightly lowered, and diatomaceous earth was used for filtration to remove salt and catalyst, and the filtrate was cooled to After reaching room temperature, the mixture was washed with water three times, the organic phase was retained, and the aqueous phase was then extracted with ethyl acetate; after the organic phases were combined, they were dried with anhydrous magnesium sulfate, and the solvent was removed with a rotary evaporator; a small amount of dichloromethane was used to completely dissolve the solid organic matter, and then it was slowly added dropwise to the petroleum ether solution, stirred evenly, and a precipitate was precipitated. The solid was filtered to obtain the solid, and it was sequentially washed with 300 mL of anhydrous ethanol and 200 mL of petroleum ether, and dried to obtain intermediate 1 (8.18 g, yield: 81.34%);

[0089] The intermediate 1 (23.85 mmol) and the raw material C-9 (23.85 mmol) were dissolved in a toluene solution, and then ventilated 3 times. Tri(dibenzylideneacetone)dipalladium (0.24 mmol), tri-tert-butylphosphine (1.19 mmol) and sodium tert-butoxide (47.70 mmol) were added under nitrogen protection, stirred evenly, heated to 90°C, and refluxed for 5 h. After the reaction was completed, the temperature was slightly lowered, filtered using diatomaceous earth to remove salt and catalyst, and the filtrate was cooled to room temperature. After warming, wash with water three times, retain the organic phase, and then extract the aqueous phase with ethyl acetate; after combining the organic phases, dry with anhydrous magnesium sulfate, and remove the solvent with a rotary evaporator; use a small amount of dichloromethane to completely dissolve the solid organic matter, and then slowly add it dropwise to the petroleum ether solution, stir evenly, precipitate, filter to obtain the solid, rinse with 300mL of anhydrous ethanol and 200mL of petroleum ether in turn, and dry to obtain intermediate 2 (10.04g, yield: 76.24%);

[0090] The intermediate 2 (18.11 mmol) and the raw material D-9 (18.11 mmol) were dissolved in a toluene solution, and then ventilated 3 times. Tri(dibenzylideneacetone)dipalladium (0.18 mmol), tri-tert-butylphosphine (0.91 mmol) and sodium tert-butoxide (36.22 mmol) were added under nitrogen protection, stirred evenly, heated to 90°C, and refluxed for 5 hours; after the reaction was completed, the temperature was slightly lowered, diatomaceous earth was used for filtration to remove salt and catalyst, and the filtrate was cooled to room temperature and washed with water three times, the organic phase was retained, and then the aqueous phase was extracted with ethyl acetate; after the organic phases were combined, they were dried with anhydrous magnesium sulfate, and the solvent was removed with a rotary evaporator; the remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V dichloromethane: V petroleum ether = 10:4) to obtain compound 9. (8.69 g, yield, 70.08%, Mw: 684.90)

[0091] The obtained compound 9 was tested and analyzed, and the results were as follows:

[0092] HPLC purity: >99%.

[0093] Mass spectrometry test: theoretical value is 684.90; tested value is 684.66.

[0094] Elemental Analysis:

[0095] Calculated values: C, 85.93; H, 5.30; N, 4.09; S, 4.68.

[0096] The test values ​​are: C, 85.51; H, 5.58; N, 4.25; S, 4.79.

[0097] H NMR spectrum: Figure 1 shown.

[0098] Example 2

[0099]

[0100] The raw material A-83 (30.00 mmol) and the raw material B-83 (30.00 mmol) were dissolved in a toluene solution, and then ventilated 3 times. Tri(dibenzylideneacetone)dipalladium (0.30 mmol), tri-tert-butylphosphine (1.50 mmol) and sodium tert-butoxide (60.00 mmol) were added under nitrogen protection, stirred evenly, heated to 90°C, and refluxed for 5 hours. After the reaction was completed, the temperature was slightly lowered, and diatomaceous earth was used for filtration to remove salt and catalyst, and the filtrate was cooled. After reaching room temperature, the mixture was washed with water three times, the organic phase was retained, and the aqueous phase was extracted with ethyl acetate; after the organic phases were combined, they were dried with anhydrous magnesium sulfate, and the solvent was removed with a rotary evaporator; a small amount of dichloromethane was used to completely dissolve the solid organic matter, and then it was slowly added dropwise to the petroleum ether solution, stirred evenly, and a precipitate was precipitated. The solid was filtered out, and it was rinsed with 300 mL of anhydrous ethanol and 200 mL of petroleum ether in turn, and dried to obtain intermediate 1 (9.70 g, yield: 75.93%);

[0101] The intermediate 1 (21.15 mmol) and the raw material C-83 (21.15 mmol) were dissolved in a toluene solution, and then ventilated 3 times. Tri(dibenzylideneacetone)dipalladium (0.21 mmol), tri-tert-butylphosphine (1.06 mmol) and sodium tert-butoxide (42.30 mmol) were added under nitrogen protection, stirred evenly, heated to 90°C, and refluxed for 5 hours. After the reaction was completed, the temperature was slightly lowered, and diatomaceous earth was used for filtration to remove salt and catalyst, and the filtrate was cooled to After reaching room temperature, the mixture was washed with water three times, the organic phase was retained, and the aqueous phase was then extracted with ethyl acetate; after the organic phases were combined, they were dried with anhydrous magnesium sulfate, and the solvent was removed with a rotary evaporator; a small amount of dichloromethane was used to completely dissolve the solid organic matter, and then slowly added dropwise to the petroleum ether solution, stirred evenly, a precipitate was precipitated, and the solid was filtered out, and it was rinsed with 300 mL of anhydrous ethanol and 200 mL of petroleum ether in turn, and dried to obtain intermediate 2 (9.55 g, yield: 72.11%);

[0102] The intermediate 2 (14.37 mmol) and the raw material D-83 (14.37 mmol) were dissolved in a toluene solution, and then ventilated 3 times. Tri(dibenzylideneacetone)dipalladium (0.14 mmol), tri-tert-butylphosphine (0.72 mmol) and sodium tert-butoxide (28.74 mmol) were added under nitrogen protection, stirred evenly, heated to 90°C, and refluxed for 5 hours; after the reaction was completed, the temperature was slightly lowered, and diatomaceous earth was used for filtration to remove salt and catalyst. After the filtrate was cooled to room temperature, it was washed with water three times, the organic phase was retained, and then the aqueous phase was extracted with ethyl acetate; after the organic phases were combined, they were dried with anhydrous magnesium sulfate, and the solvent was removed with a rotary evaporator; the remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V dichloromethane: V petroleum ether = 10:4) to obtain compound 83. (7.24 g, yield, 66.35%, Mw: 758.92)

[0103] The obtained compound 83 was tested and analyzed, and the results were as follows:

[0104] HPLC purity: >99%.

[0105] Mass spectrometry test: theoretical value is 758.92; tested value is 758.59.

[0106] Elemental Analysis:

[0107] Calculated values: C, 87.05; H, 5.05; N, 3.69; O, 4.22.

[0108] The test values ​​are: C, 86.64; H, 5.27; N, 3.91; O, 4.40.

[0109] H NMR spectrum: Figure 2 shown.

[0110] Example 3

[0111]

[0112] The raw material A-119 (30.00 mmol) and the raw material B-119 (30.00 mmol) were dissolved in a toluene solution, and then ventilated 3 times. Tri(dibenzylideneacetone)dipalladium (0.30 mmol), tri-tert-butylphosphine (1.50 mmol) and sodium tert-butoxide (60.00 mmol) were added under nitrogen protection, stirred evenly, heated to 90°C, and refluxed for 5 hours. After the reaction was completed, the temperature was slightly lowered, and diatomaceous earth was used for filtration to remove salt and catalyst, and the filtrate was cooled. After cooling to room temperature, the mixture was washed with water three times, the organic phase was retained, and the aqueous phase was extracted with ethyl acetate; after the organic phases were combined, they were dried with anhydrous magnesium sulfate, and the solvent was removed with a rotary evaporator; a small amount of dichloromethane was used to completely dissolve the solid organic matter, and then it was slowly added dropwise to the petroleum ether solution, stirred evenly, and a precipitate was precipitated. The solid was filtered to obtain the solid, and it was washed with 300 mL of anhydrous ethanol and 200 mL of petroleum ether in turn, and dried to obtain intermediate 1 (9.68 g, yield: 78.39%);

[0113] The intermediate 1 (21.87 mmol) and the raw material C-119 (21.87 mmol) were dissolved in a toluene solution, and then ventilated 3 times. Tri(dibenzylideneacetone)dipalladium (0.22 mmol), tri-tert-butylphosphine (1.09 mmol) and sodium tert-butoxide (43.74 mmol) were added under nitrogen protection, stirred evenly, heated to 90°C, and refluxed for 5 hours. After the reaction was completed, the temperature was slightly lowered, filtered using diatomaceous earth to remove salt and catalyst, and the filtrate was cooled. After reaching room temperature, the mixture was washed with water three times, the organic phase was retained, and the aqueous phase was then extracted with ethyl acetate; after the organic phases were combined, they were dried with anhydrous magnesium sulfate, and the solvent was removed with a rotary evaporator; a small amount of dichloromethane was used to completely dissolve the solid organic matter, and then it was slowly added dropwise to the petroleum ether solution, stirred evenly, and a precipitate was precipitated. The solid was filtered to obtain the solid, and it was washed with 300 mL of anhydrous ethanol and 200 mL of petroleum ether in turn, and dried to obtain intermediate 2 (9.60 g, yield: 69.87%);

[0114] The intermediate 2 (14.33 mmol) and the raw material D-119 (14.33 mmol) were dissolved in a toluene solution, and then ventilated 3 times. Tri(dibenzylideneacetone)dipalladium (0.14 mmol), tri-tert-butylphosphine (0.72 mmol) and sodium tert-butoxide (28.66 mmol) were added under nitrogen protection, stirred evenly, heated to 90°C, and refluxed for 5 hours; after the reaction was completed, the temperature was slightly lowered, and diatomaceous earth was used for filtration to remove salt and catalyst. After the filtrate was cooled to room temperature, it was washed with water three times, the organic phase was retained, and then the aqueous phase was extracted with ethyl acetate; after the organic phases were combined, they were dried with anhydrous magnesium sulfate, and the solvent was removed with a rotary evaporator; the remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V dichloromethane: V petroleum ether = 10:4) to obtain compound 119. (6.97 g, yield, 63.87%, Mw: 761.00)

[0115] The obtained compound 119 was tested and analyzed, and the results were as follows:

[0116] HPLC purity: >99%.

[0117] Mass spectrometry test: theoretical value is 761.00; tested value is 760.69.

[0118] Elemental Analysis:

[0119] Calculated values: C, 86.81; H, 5.30; N, 3.68; S, 4.21.

[0120] The test values ​​are: C, 86.59; H, 5.53; N, 3.81; S, 4.45.

[0121] H NMR spectrum: Figure 3 shown.

[0122] Example 4

[0123]

[0124] The raw material A-238 (30.00 mmol) and the raw material B-238 (30.00 mmol) were dissolved in a toluene solution, and then ventilated 3 times. Tri(dibenzylideneacetone)dipalladium (0.30 mmol), tri-tert-butylphosphine (1.50 mmol) and sodium tert-butoxide (60.00 mmol) were added under nitrogen protection, stirred evenly, heated to 90°C, and refluxed for 5 hours. After the reaction was completed, the temperature was slightly lowered, and diatomaceous earth was used for filtration to remove salt and catalyst, and the filtrate was cooled. After cooling to room temperature, the mixture was washed with water three times, the organic phase was retained, and the aqueous phase was extracted with ethyl acetate; after the organic phases were combined, they were dried with anhydrous magnesium sulfate, and the solvent was removed with a rotary evaporator; a small amount of dichloromethane was used to completely dissolve the solid organic matter, and then it was slowly added dropwise to the petroleum ether solution, stirred evenly, and a precipitate was precipitated. The solid was filtered out, and it was washed with 300 mL of anhydrous ethanol and 200 mL of petroleum ether in turn, and dried to obtain intermediate 1 (8.12 g, yield: 70.14%);

[0125] The intermediate 1 (20.75 mmol) and the raw material C-238 (20.75 mmol) were dissolved in a toluene solution, and then ventilated 3 times. Tri(dibenzylideneacetone)dipalladium (0.21 mmol), tri-tert-butylphosphine (1.04 mmol) and sodium tert-butoxide (41.50 mmol) were added under nitrogen protection, stirred evenly, heated to 90°C, and refluxed for 5 hours. After the reaction was completed, the temperature was slightly lowered, filtered using diatomaceous earth to remove salt and catalyst, and the filtrate was cooled. After reaching room temperature, the mixture was washed with water three times, the organic phase was retained, and the aqueous phase was then extracted with ethyl acetate; after the organic phases were combined, they were dried with anhydrous magnesium sulfate, and the solvent was removed with a rotary evaporator; a small amount of dichloromethane was used to completely dissolve the solid organic matter, and then slowly added dropwise to the petroleum ether solution, stirred evenly, a precipitate was precipitated, and the solid was filtered out, and it was rinsed with 300 mL of anhydrous ethanol and 200 mL of petroleum ether in turn, and dried to obtain intermediate 2 (8.67 g, yield: 70.94%);

[0126] The intermediate 2 (13.28 mmol) and the raw material D-238 (13.28 mmol) were dissolved in a toluene solution, and then ventilated 3 times. Tri(dibenzylideneacetone)dipalladium (0.13 mmol), tri-tert-butylphosphine (0.66 mmol) and sodium tert-butoxide (26.56 mmol) were added under nitrogen protection, stirred evenly, heated to 90°C, and refluxed for 5 hours; after the reaction was completed, the temperature was slightly lowered, and diatomaceous earth was used for filtration to remove salt and catalyst. After the filtrate was cooled to room temperature, it was washed with water three times, the organic phase was retained, and then the aqueous phase was extracted with ethyl acetate; after the organic phases were combined, they were dried with anhydrous magnesium sulfate, and the solvent was removed with a rotary evaporator; the remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V dichloromethane: V petroleum ether = 10:4) to obtain compound 238. (5.90 g, yield, 60.44%, Mw: 734.96)

[0127] The obtained compound 238 was tested and analyzed, and the results were as follows:

[0128] HPLC purity: >99%.

[0129] Mass spectrometry test: theoretical value is 734.96; tested value is 734.67.

[0130] Elemental Analysis:

[0131] Calculated values: C, 86.61; H, 5.21; N, 3.81; S, 4.36.

[0132] The test values ​​are: C, 86.39; H, 5.42; N, 4.00; S, 4.58.

[0133] H NMR spectrum: Figure 4 shown.

[0134] Since the general structural formula is the chemical formula I in the content of the invention, the synthesis routes and principles of other compounds are the same as those of the above-listed embodiments. Among them, Examples 5 to 65 of the present application can obtain the luminescent auxiliary materials shown in Table 1 below according to the above preparation method:

[0135] Table 1

[0136]

[0137]

[0138]

[0139] The organic electroluminescent device is prepared by using the luminescence auxiliary material provided in the above embodiment. When the organic layer includes a luminescence auxiliary layer, the luminescence auxiliary layer includes the luminescence auxiliary material provided in the above embodiment.

[0140] Device Example 1: Preparation of red organic electroluminescent device

[0141] The structure of the prepared OLED device is: ITO anode / HIL / HTL / luminescent auxiliary layer / EML / HBL / ETL / EIL / cathode / light extraction layer

[0142] a. ITO anode: the coating thickness is The ITO (indium tin oxide)-Ag-ITO (indium tin oxide) glass substrate was cleaned twice in distilled water, ultrasonically cleaned for 30 minutes, and then repeatedly cleaned twice with distilled water, ultrasonically cleaned for 10 minutes. After washing, it was ultrasonically cleaned with methanol, acetone, and isopropanol in sequence (5 minutes each time), dried, and then transferred to a plasma cleaning machine for washing for 5 minutes. It was then sent to a vapor deposition machine, and the substrate was used as the anode, and other functional layers were deposited thereon in sequence.

[0143] b. HIL (hole injection layer): The hole injection layer materials HT-1 and P-dopant are vacuum evaporated at a deposition rate of 97:3, and the thickness is 10 nm;

[0144] c. HTL (hole transport layer): At a deposition rate of 100%, 130 nm of HT-1 was vacuum-deposited on the hole injection layer as a hole transport layer.

[0145] d. Light-emitting auxiliary layer: At a deposition rate of , 10 nm of the compound 2 provided in the above embodiment is vacuum-deposited on the hole transport layer as a light-emitting auxiliary layer;

[0146] e. EML (light-emitting layer): Then on the above-mentioned light-emitting auxiliary layer, The evaporation rate of the main material (Host-1) and the dopant material (Dopant-1) with a thickness of 20nm are vacuum evaporated as the light-emitting layer. The chemical formulas of Host-1 and Dopant-1 are shown below. The evaporation rate ratio of the double Host-1 and Dopant-1 is 98:2.

[0147] 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 .

[0148] 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.

[0149] 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.

[0150] 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.

[0151] 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.

[0152] K. Then the vapor-deposited substrate is packaged. First, the cleaned cover is coated with UV glue using glue coating equipment, and then the coated cover is moved to the pressing section, the vapor-deposited substrate is placed on the upper end of the cover, and finally the substrate and cover are bonded by bonding equipment, and the UV glue is cured by light.

[0153]

[0154] Referring to the method provided in the above device embodiment 1, compounds 4, 8, 9, 13, 21, 22, 23, 24, 26, 27, 34, 37, 38, 42, 44, 48, 50, 53, 54, 55, 65, 66, 67, 68, 69, 70, 71, 73, 80, 83, 93, 94, 99, 101, 102, 105, 106, 114, 115, 116 9, 120, 122, 125, 126, 129, 139, 156, 183, 189, 190, 192, 212, 224, 226, 229, 230, 231, 233, 238, 274, 280, 281, 284, and 285 are used to replace compound 2, and the light-emitting auxiliary layer is evaporated to prepare the corresponding organic electroluminescent devices, which are respectively recorded as device embodiments 2 to 65.

[0155] Device Comparison Example 1:

[0156] This comparative example provides an organic electroluminescent device, the only difference between the preparation method of the organic electroluminescent device and the device embodiment 1 is that the organic electroluminescent device uses the existing comparative compound a to replace the luminescent auxiliary material (compound 2) in the above device embodiment 1 for evaporation. The chemical structure of the comparative compound a is shown below.

[0157] Device Comparison Example 2:

[0158] This comparative example provides an organic electroluminescent device, and the only difference between the preparation method of the organic electroluminescent device and the device embodiment 1 is that the organic electroluminescent device uses the existing comparative compound b to replace the luminescent auxiliary material (compound 2) in the above device embodiment 1 for evaporation. The chemical structure of the comparative compound b is shown below.

[0159] Device Comparison Example 3:

[0160] This comparative example provides an organic electroluminescent device, and the only difference between the preparation method of the organic electroluminescent device and the device embodiment 1 is that the organic electroluminescent device uses the existing comparative compound c to replace the luminescent auxiliary material (compound 2) in the above device embodiment 1 for evaporation. The chemical structure of the comparative compound c is shown below.

[0161]

[0162] The driving voltage, luminous efficiency and life of the organic electroluminescent devices obtained from the device embodiments 1 to 65 and the device comparative examples 1 to 3 were characterized at a brightness of 6000 (nits). The test results are shown in Table 2 below:

[0163] Table 2

[0164]

[0165]

[0166]

[0167] It can be seen from Table 2 that the performance of the device can be changed by changing the substituents and the positions of the substituents. Compared with the existing organic electroluminescent devices provided by the comparative example compounds, the luminous efficiency and life of the organic electroluminescent device prepared using the luminescent auxiliary material provided by the present application are improved.

[0168] 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 luminescent auxiliary material, characterized in that: The general structural formula of the luminescence auxiliary material is shown in Chemical Formula I: X is selected from one of O and S; Y is selected from one of a connecting bond, C(R6, R7), O, S, and NR8; R1 independently represents one of hydrogen, deuterium, halogen, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted 3-20 membered heterocycloalkyl, wherein the heteroatom is N, O, S, Si, P, Se; R2 and R3 independently represent hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic acid, phosphoric acid, borane, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C20 cycloalkyl except adamantyl, substituted or unsubstituted 3-20-membered heterocycloalkyl, wherein the heteroatom is N, O, S, Si, P, Se; substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-30-membered heteroaryl, wherein the heteroatom is N, O, S, Si, P, Se; wherein R2 and R3 cannot be connected to each other to form a ring; R4 and R5 independently represent hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic acid, phosphoric acid, borane, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted 3-20 membered heterocycloalkyl, wherein the heteroatom is N, O, S, Si, P, Se; substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-30 membered heteroaryl, wherein the heteroatom is N, O, S, Si, P, Se; R6, R7, and R8 independently represent hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted 3-20 membered heterocycloalkyl, wherein the heteroatom is N, O, S, Si, P, Se; substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-30 membered heteroaryl, wherein the heteroatom is N, O, S, Si, P, Se; Ar is a substituent fused to the benzene ring, and Ar can be fused to the 12th or 34th position of the benzene ring; Ar represents a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted 3-20-membered heteroaryl group, wherein the heteroatom is selected from O, N, and S; The Ar1 is one of the following structures: Ar2 independently represents a diphenylamino group.

2. The luminescence auxiliary material according to claim 1, characterized in that: The general structural formula of the luminescent auxiliary material is one of the following structures:

3. The luminescence auxiliary material according to claim 1, characterized in that: The Y is a connecting bond; and the R2 and R3 are hydrogen.

4. The luminescence auxiliary material according to claim 1, characterized in that: The Ar is a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted 3-20-membered heteroaryl group, wherein the heteroatom is N, O, S, Si, P, or Se.

5. The luminescence auxiliary material according to claim 4, characterized in that: The Ar is a phenyl group.

6. The luminescence auxiliary material according to claim 1, characterized in that: The general structural formula of the luminescent auxiliary material is one of the following structures:

7. The luminescence auxiliary material according to claim 1, characterized in that: The general structural formula of the luminescent auxiliary material is one of the following structures:

8. A method for preparing the luminescence auxiliary material according to claim 1, characterized in that: include: The raw materials A and B are dissolved in a toluene solution, tri(dibenzylideneacetone)dipalladium, tri-tert-butylphosphine and sodium tert-butoxide are added under nitrogen protection, stirred evenly, and heated to reflux for reaction to obtain intermediate 1; The intermediate 1 and the raw material C are dissolved in a toluene solution, tri(dibenzylideneacetone)dipalladium, tri-tert-butylphosphine and sodium tert-butoxide are added under nitrogen protection, stirred evenly, and heated to reflux for reaction to obtain the intermediate 2; The intermediate 2 and the raw material D are dissolved in a toluene solution, tri(dibenzylideneacetone)dipalladium, tri-tert-butylphosphine and sodium tert-butoxide are added under nitrogen protection, stirred evenly, and heated to reflux for reaction to obtain the luminescent auxiliary material shown in chemical formula I.

9. A light emitting device, characterized in that: The light-emitting device comprises the light-emitting auxiliary material according to any one of claims 1 to 7 or the light-emitting auxiliary material prepared by the method for preparing the light-emitting auxiliary material according to claim 8.

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