CN115181074A - Luminous auxiliary material, preparation method thereof and luminous device - Google Patents

Luminous auxiliary material, preparation method thereof and luminous device Download PDF

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CN115181074A
CN115181074A CN202210658885.9A CN202210658885A CN115181074A CN 115181074 A CN115181074 A CN 115181074A CN 202210658885 A CN202210658885 A CN 202210658885A CN 115181074 A CN115181074 A CN 115181074A
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heteroatom
auxiliary material
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汪康
贾宇
陈振生
孙向南
马晓宇
黄悦
于丹阳
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The application is suitable for the technical field of materials, and provides a luminescent auxiliary material, a preparation method thereof and a luminescent device, wherein the luminescent auxiliary material is used as a luminescent auxiliary material of an organic electroluminescent device by limiting the types of connecting groups connected with a core, the types of amino groups bonded with the connecting groups and characteristic compounds of bonding positions, so that the hole transmission efficiency and the electron blocking capacity are improved to a great extent, the charges of holes and electrons in a luminescent layer are increased in a balanced manner, and therefore, the luminescent efficiency and the service life of the organic electroluminescent device are improved by easily realizing the HOMO energy level of charge balance in the luminescent layer instead of the surface of a hole transport layer.

Description

Luminous auxiliary material, preparation method thereof and luminous device
Technical Field
The application belongs to the technical field of materials, and particularly relates to a luminous auxiliary material, a preparation method thereof and a luminous device.
Background
Generally, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic substance. An organic light emitting device using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, a fast response time, and excellent luminance, driving voltage, and response speed characteristics, and thus a great deal of research is being conducted. Many improvements have been made to make organic EL devices practical. For example, it is known that high efficiency and high durability can be achieved by further distributing various functions 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 provided on a substrate. With this organic EL device, charges injected from the two electrodes are recombined in the light emitting layer to obtain light emission. In this case, how to efficiently transfer charges of holes and electrons to the light emitting layer is important, and the device is required to have excellent carrier balance. Also, the light emitting efficiency is improved by enhancing a hole injecting property and an electron blocking property of blocking electrons injected from the cathode to increase a recombination probability of holes and electrons, and by confining excitons generated in the light emitting layer. Therefore, the role of the luminescence assisting material is so important.
The research on organic electroluminescent materials has been widely carried out in academia and industry, but the development of stable and efficient organic layer materials for organic electronic devices has not been fully developed so far, and the industrialization of the technology still faces many key problems, so that the development of new materials is a problem to be solved by those skilled in the art.
Disclosure of Invention
The application aims to provide a luminescent auxiliary material, and aims to solve the problem that the luminous efficiency and the service life improvement effect of the existing organic electroluminescent device are not obvious.
The application is realized by the following steps that the structural general formula of the luminescent auxiliary material is shown in a chemical formula I:
Figure BDA0003687728370000021
x is selected from one of O, S; y is selected from the group consisting of a connecting bond, C (R) 6 ,R 7 )、O、S、NR 8 One of (1);
R 1 independently represents one of hydrogen, deuterium, halogen, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C20 cycloalkyl and substituted or unsubstituted 3-to 20-membered heterocycloalkyl, wherein the heteroatom is N, O, S, si, P, se;
R 2 、R 3 independently represent hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic acid group, phosphoric acid group, boryl, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C20 cycloalkyl other than adamantyl, substituted or unsubstituted 3-to 20-membered heterocycloalkyl wherein the heteroatom is N, O, S, si, P, se, or the like; one of substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, whichThe middle heteroatom is N, O, S, si, P, se; wherein R is 2 、R 3 Can not be connected with each other to form a ring;
R 4 、R 5 independently represent hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic acid group, phosphoric acid group, boryl, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted 3-to 20-membered heterocycloalkyl, wherein the heteroatom is N, O, S, si, P, se; one of substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted 3-to 30-membered heteroaryl, wherein the heteroatom is N, O, S, si, P, se;
R 6 、R 7 、R 8 independently represent hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted 3-to 20-membered heterocycloalkyl, wherein the heteroatom is N, O, S, si, P, se, or the like; one of substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted 3-to 30-membered heteroaryl, wherein the heteroatom is N, O, S, si, P, se;
ar is a substituent fused on a benzene ring, and Ar may be fused at the 12-position or 34-position of the benzene ring.
Ar represents a substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 20-membered heteroaryl, the heteroatom of which is selected from O, N, S;
Ar 1 independently represent substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3-to 30-membered heterocycloalkyl, wherein the heteroatom is N, O, S, si, P, se; substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, wherein the heteroatom is N, O, S, si, P, se; a substituted or unsubstituted C10-C30 fused ring group;
Ar 2 independently represented as a dianilino group.
Another object of the present application is a method for preparing a luminescence support material, comprising:
Figure BDA0003687728370000031
dissolving a raw material A and a raw material B in a toluene solution, adding tris (dibenzylideneacetone) dipalladium, tri-tert-butylphosphine and sodium tert-butoxide under the protection of nitrogen, uniformly stirring, and heating to reflux for reaction to obtain an intermediate 1;
dissolving the intermediate 1 and the raw material C in a toluene solution, adding tris (dibenzylideneacetone) dipalladium, tri-tert-butylphosphine and sodium tert-butoxide under the protection of nitrogen, stirring uniformly, and heating to reflux for reaction to obtain an intermediate 2;
and dissolving the intermediate 2 and the raw material D in a toluene solution, adding tris (dibenzylideneacetone) dipalladium, tri-tert-butylphosphine and sodium tert-butoxide under the protection of nitrogen, uniformly stirring, and heating to reflux for reaction to obtain the luminescence auxiliary material shown in the chemical formula I.
Another object of the present application is to a light emitting device comprising the luminescence assistant material or the luminescence assistant material prepared according to the method for preparing the luminescence assistant material.
The light-emitting auxiliary material provided by the application is used as a light-emitting auxiliary material of an organic electroluminescent device by limiting the types of the connecting groups connected with the core, the types of the amino groups bonded with the connecting groups and the characteristic compounds of the bonding positions, the hole transmission efficiency is greatly improved, the electron blocking capacity is improved, the charge balance of holes and electrons in a light-emitting layer is increased, and therefore the light is not emitted on the surface of a hole transport layer but is well formed in the light-emitting layer, and the light-emitting efficiency and the service life of the organic electroluminescent device are improved by easily realizing the HOMO energy level of the charge balance in the light-emitting layer.
Drawings
Figure 1 is a nuclear magnetic resonance hydrogen spectrum of compound 9 provided in example 1 of the present application;
FIG. 2 is a NMR spectrum of Compound 83 provided in example 2 herein;
figure 3 is a nuclear magnetic resonance hydrogen spectrum of compound 119 provided in example 3 of the present application;
fig. 4 is a nmr hydrogen spectrum of compound 238 provided in example 4 herein.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of and not restrictive on the broad application.
The application provides a luminescent auxiliary material, which has a structural general formula shown as a chemical formula I:
Figure BDA0003687728370000051
in formula I:
x is selected from O and S; y is selected from the group consisting of a connecting bond, C (R6, R7), O, S, NR;
R 1 independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C25) alkyl, substituted or unsubstituted (C3-C20) cycloalkyl, substituted or unsubstituted (3-to 20-membered) heterocycloalkyl, wherein the heteroatom is N, O, S, si, P, se, or the like;
R 2 、R 3 independently represent hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic acid group, phosphoric acid group, boryl, substituted or unsubstituted (C1-C25) alkyl, substituted or unsubstituted (C3-C20) cycloalkyl (except adamantyl), substituted or unsubstituted (3-to 20-membered) heterocycloalkyl, wherein the heteroatom is N, O, S, si, P, se, or the like; one of 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.; wherein R is 2 、R 3 Cannot be connected to each other to form a ring.
R 4 、R 5 Independently represent hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic acid group, phosphoric acid group, boryl, substituted or unsubstituted (C1-C25) alkyl, substituted or unsubstituted (C3-C20) cycloalkyl, substituted or unsubstituted (3-to 20-membered) heterocycloalkyl, wherein the heteroatom is N, O, S, si, P, se, or the like; substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-to 30-membered)) One of heteroaryl, wherein the heteroatom is N, O, S, si, P, se, etc.;
R 6 、R 7 、R 8 independently represent hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C20) alkyl, substituted or unsubstituted (C3-C20) cycloalkyl, substituted or unsubstituted (3-to 20-membered) heterocycloalkyl, wherein the heteroatom is N, O, S, si, P, se, or the like; one of 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.;
ar is a substituent fused on a benzene ring, and Ar may be fused at the 12-position or 34-position of the benzene ring.
Ar represents a substituted or unsubstituted (C6-C30) aryl, a substituted or unsubstituted (3-to 20-membered) heteroaryl, the heteroatoms of which are selected from oxygen (O), nitrogen (N), sulphur (S);
Ar 1 independently represent substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (3-to 30-membered) heterocycloalkyl, wherein the heteroatoms are 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, or the like; a substituted or unsubstituted (C10-C30) fused ring group;
Ar 2 independently represented by a diphenylamine group;
the preferred general structural formula of formula I above is:
Figure BDA0003687728370000061
wherein X, Y, R to R5, ar1 and Ar2 in the above chemical formulas-I-a to-I-b are as defined above.
Further preferably, Y is selected from a connecting bond;
further preferably, R 2 、R 3 Represents hydrogen;
further preferably, ar represents a substituted or unsubstituted (C6-C20) aryl group, a substituted or unsubstituted (3-to 20-membered) heteroaryl group in which the heteroatom is N, O, S, si, P, se, or the like;
even more preferably, ar is phenyl;
further preferably, ar is 1 Represents:
Figure BDA0003687728370000071
the more preferred general structural formula of formula I above is:
Figure BDA0003687728370000081
Figure BDA0003687728370000091
in the above technical solutions, the term "substituted or unsubstituted" means substituted by one, two or more substituents selected from: hydrogen; deuterium; a halogen group; a nitrile group; C1-C5 alkyl; C6-C20 aryl; a C6-C18 heteroaryl; or a substituent in which two or more substituents among the above-shown substituents are linked, or no substituent. For example, "a substituent in which two or more substituents are linked" may include a biphenyl group. In other words, biphenyl can be an aryl group, or can be interpreted as a substituent with two phenyl groups attached.
In the above technical solution, it is further preferable that the luminescence auxiliary material is any one of the following structures, but is not limited thereto:
Figure BDA0003687728370000111
Figure BDA0003687728370000121
Figure BDA0003687728370000131
Figure BDA0003687728370000141
Figure BDA0003687728370000151
Figure BDA0003687728370000161
Figure BDA0003687728370000171
Figure BDA0003687728370000181
Figure BDA0003687728370000191
another object of the present invention is to provide a method for preparing the above luminescent auxiliary material, preferably by the following reaction scheme.
Scheme 1:
Figure BDA0003687728370000201
step 1, preparation of intermediate 1
Dissolving a raw material A (1.0 eq) and a raw material B (1.0 eq) in a toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.01 eq), tri-tert-butylphosphine (0.05 eq) and sodium tert-butoxide (2.0 eq) under the protection of nitrogen, stirring uniformly, heating to reflux, and reacting for 5 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 1;
step 2, preparation of intermediate 2
Dissolving the intermediate 1 (1.0 eq) and the raw material C (1.0 eq) in a toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.01 eq), tri-tert-butylphosphine (0.05 eq) and sodium tert-butoxide (2.0 eq) under the protection of nitrogen, stirring uniformly, heating to reflux, and reacting for 5 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 2;
step 3, preparation of intermediate 3
Dissolving the intermediate 2 (1.0 eq) and the raw material D (1.0 eq) in a toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.01 eq), tri-tert-butylphosphine (0.05 eq) and sodium tert-butoxide (2.0 eq) under the protection of nitrogen, stirring uniformly, heating to reflux, and reacting for 5 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V dichloromethane: V petroleum ether = 10) to obtain formula I.
Wherein X, Y, ar 1 、Ar 2 、R 1 ～R 5 As defined above in formula I.
It is another object of embodiments of the present application to provide a light emitting device including a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode.
The organic material layer of the light emitting device of the present disclosure may be formed in a single layer structure, but may also be formed in a multi-layer structure in which a layer and two or more organic material layers are present. 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, and the like as organic material layers. However, the structure of the light emitting device is not limited thereto, and a smaller number of organic material layers or a larger number of organic material layers may be included.
As the anode material, a material having a large work function is generally preferred so that holes are 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 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.
The hole injecting material is a material that advantageously receives holes from the anode at low voltages, and the Highest Occupied Molecular Orbital (HOMO) of the hole injecting material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metalloporphyrins, oligothiophenes, arylamine-based organic materials, hexanenitrile-based organic materials, quinacridone-based organic materials, perylene-based organic materials, anthraquinones, and polyaniline-based and polythiophene-based conductive polymers, and the like, but are not limited thereto, and may further include additional compounds capable of p-doping.
The hole transport material is a material capable of receiving holes from the anode or the hole injection layer and transporting the holes to the light emitting layer, and a material having high hole mobility is suitable. Specific examples thereof include arylamine-based organic materials, conductive polymers, block copolymers having both conjugated portions and non-conjugated portions, and the like, but are not limited thereto.
The light emitting layer may emit red, green or blue light, and may be formed of a phosphorescent material or a fluorescent material. The light emitting material is a material capable of emitting light in a visible light region by receiving holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining the holes and the electrons, and is preferably a material having favorable quantum efficiency for fluorescence or phosphorescence. Specific examples thereof include: 8-hydroxyquinoline aluminum complex (Alq 3); a carbazole-based compound; a di-polystyrene based compound; BAlq; 10-hydroxybenzoquinoline-metal compounds; benzocarbazole-, benzothiazole-, and benzimidazole-based compounds; polymers based on poly (p-phenylene vinylene) (PPV); a spiro compound; a polyfluorene; rubrene, and the like, but is not limited thereto.
The host material of the light-emitting layer includes a condensed aromatic ring derivative, a heterocyclic ring-containing compound, and the like. Specifically, the fused aromatic ring derivative includes an anthracene derivative, a pyrene derivative, a naphthalene derivative, a pentacene derivative, a phenanthrene compound, a fluoranthene compound, and the like, and the heterocycle-containing compound includes a carbazole derivative, a dibenzofuran derivative, a ladder-type furan compound, a pyrimidine derivative, and the like, however, the material is not limited thereto.
The electron transport layer may function to facilitate electron transport. The electron transport material is a material that favorably receives electrons from the cathode and transports the electrons to the light emitting layer, and a material having high electron mobility is suitable. Specific examples thereof include: al complexes of 8-hydroxyquinoline; a complex comprising Alq 3; an organic radical compound; a hydroxyflavone-metal complex; and the like, but is not limited thereto. The thickness of the electron transport layer may be 1nm to 50nm. The electron transport layer having a thickness of 1nm or more has an advantage of preventing the electron transport property from being degraded, and the electron transport layer having a thickness of 50nm or less has an advantage of preventing the driving voltage for enhancing electron transfer from being increased due to the electron transport layer being too thick.
The electron injection layer may function to promote electron injection. The electron-injecting material is preferably a compound of: it has an ability to transport electrons, has an electron injection effect from a cathode, has an excellent electron injection effect on a light emitting layer or a light emitting material, prevents excitons generated in the light emitting layer from migrating to a hole injection layer, and, in addition, has an excellent thin film forming ability. Specific examples thereof include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like and derivatives thereof, metal complexes, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.
As the cathode material, a material having a small work function is generally preferred so that electrons are smoothly injected into the organic material layer. Specific examples of the cathode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer materials, such as LiF/Al or LiO2/Al; and the like, but are not limited thereto.
The light emitting device provided herein may be applied to an Organic Light Emitting Device (OLED), an Organic Solar Cell (OSC), an electronic paper (e-paper), an Organic Photoreceptor (OPC), or an Organic Thin Film Transistor (OTFT).
The technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the luminescent auxiliary material of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments.
In addition, it should be noted that the numerical values given in the following examples are as precise as possible, but those skilled in the art will understand that each numerical value should be understood as a divisor rather than an absolutely exact numerical value due to measurement errors and experimental operational problems that cannot be avoided.
Example 1
Figure BDA0003687728370000241
Dissolving a raw material A-9 (30.00 mmol) and a raw material B-9 (30.00 mmol) in a toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.30 mmol), tri-tert-butylphosphine (1.50 mmol) and sodium tert-butoxide (60.00 mmol) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, and carrying out reflux reaction for 5 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching with 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 1 (8.18 g, yield: 81.34%);
dissolving the intermediate 1 (23.85 mmol) and the raw material C-9 (23.85 mmol) in a toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.24 mmol), tri-tert-butylphosphine (1.19 mmol) and sodium tert-butoxide (47.70 mmol) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, and carrying out reflux reaction for 5 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching with 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 2 (10.04 g, yield: 76.24%);
dissolving the intermediate 2 (18.11 mmol) and the raw material D-9 (18.11 mmol) in a toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.18 mmol), tri-tert-butylphosphine (0.91 mmol) and sodium tert-butoxide (36.22 mmol) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, and carrying out reflux reaction for 5 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salts and a catalyst, cooling the filtrate to room temperature, washing for three times by using water, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using 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) to obtain compound 9. (8.69 g, yield, 70.08%, mw: 684.90)
The compound 9 obtained was subjected to detection analysis, and the results were as follows:
HPLC purity: is more than 99 percent.
Mass spectrum testing: theoretical value is 684.90; the test value was 684.66.
Elemental analysis:
the calculated values are: c,85.93; h,5.30; n,4.09; and S,4.68.
The test values are: c,85.51; h,5.58; n,4.25; s,4.79.
Nuclear magnetic resonance hydrogen spectrum: as shown in fig. 1.
Example 2
Figure BDA0003687728370000261
Dissolving a raw material A-83 (30.00 mmol) and a raw material B-83 (30.00 mmol) in a toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.30 mmol), tri-tert-butylphosphine (1.50 mmol) and sodium tert-butoxide (60.00 mmol) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, and carrying out reflux reaction for 5 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching with 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 1 (9.70 g, yield: 75.93%);
dissolving the intermediate 1 (21.15 mmol) and the raw material C-83 (21.15 mmol) in a toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.21 mmol), tri-tert-butylphosphine (1.06 mmol) and sodium tert-butoxide (42.30 mmol) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, and carrying out reflux reaction for 5 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 2 (9.55 g, yield: 72.11%);
dissolving the intermediate 2 (14.37 mmol) and the raw material D-83 (14.37 mmol) in a toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.14 mmol), tri-tert-butylphosphine (0.72 mmol) and sodium tert-butoxide (28.74 mmol) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, and carrying out reflux reaction for 5 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using 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) to obtain compound 83. (7.24 g, yield, 66.35%, mw: 758.92)
The detection analysis of the obtained compound 83 was carried out, and the results were as follows:
HPLC purity: is more than 99 percent.
Mass spectrometry test: theoretical value 758.92; the test value was 758.59.
Elemental analysis:
the calculated values are: c,87.05; h,5.05; n,3.69; and O,4.22.
The test values are: c,86.64; h,5.27; n,3.91; o,4.40.
Nuclear magnetic resonance hydrogen spectrum: as shown in fig. 2.
Example 3
Figure BDA0003687728370000271
Dissolving a raw material A-119 (30.00 mmol) and a raw material B-119 (30.00 mmol) in a toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.30 mmol), tri-tert-butylphosphine (1.50 mmol) and sodium tert-butoxide (60.00 mmol) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, and carrying out reflux reaction for 5 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dripping the dissolved solid organic matter into petroleum ether solution, uniformly stirring, separating out precipitate, performing suction filtration to obtain solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 1 (9.68 g, yield: 78.39%);
dissolving the intermediate 1 (21.87 mmol) and the raw material C-119 (21.87 mmol) in a toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.22 mmol), tri-tert-butylphosphine (1.09 mmol) and sodium tert-butoxide (43.74 mmol) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, and carrying out reflux reaction for 5 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching with 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 2 (9.60 g, yield: 69.87%);
dissolving the intermediate 2 (14.33 mmol) and the raw material D-119 (14.33 mmol) in a toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.14 mmol), tri-tert-butylphosphine (0.72 mmol) and sodium tert-butoxide (28.66 mmol) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, and carrying out reflux reaction for 5 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using 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) to obtain compound 119. (6.97 g, yield, 63.87%, mw: 761.00)
The detection analysis of the obtained compound 119 was carried out as follows:
HPLC purity: is more than 99 percent.
Mass spectrometry test: theoretical value is 761.00; the test value was 760.69.
Elemental analysis:
the calculated values are: c,86.81; h,5.30; n,3.68; s,4.21.
The test values are: c,86.59; h,5.53; n,3.81; s,4.45.
Nuclear magnetic resonance hydrogen spectrum: as shown in fig. 3.
Example 4
Figure BDA0003687728370000291
Dissolving a raw material A-238 (30.00 mmol) and a raw material B-238 (30.00 mmol) in a toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.30 mmol), tri-tert-butylphosphine (1.50 mmol) and sodium tert-butoxide (60.00 mmol) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, and carrying out reflux reaction for 5 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 1 (8.12 g, yield: 70.14%);
dissolving the intermediate 1 (20.75 mmol) and the raw material C-238 (20.75 mmol) in a toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.21 mmol), tri-tert-butylphosphine (1.04 mmol) and sodium tert-butoxide (41.50 mmol) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, and carrying out reflux reaction for 5 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator; completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching with 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 2 (8.67 g, yield: 70.94%);
dissolving the intermediate 2 (13.28 mmol) and the raw material D-238 (13.28 mmol) in a toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.13 mmol), tri-tert-butylphosphine (0.66 mmol) and sodium tert-butoxide (26.56 mmol) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, and carrying out reflux reaction for 5 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using 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) to obtain compound 238. (5.90 g, yield 60.44%, mw: 734.96)
The compound 238 thus obtained was subjected to detection analysis, and the results were as follows:
HPLC purity: is more than 99 percent.
Mass spectrum testing: theoretical value is 734.96; the test value was 734.67.
Elemental analysis:
the calculated values are: c,86.61; h,5.21; n,3.81; and S,4.36.
The test values are: c,86.39; h,5.42; n,4.00; and S,4.58.
Nuclear magnetic resonance hydrogen spectrum: as shown in fig. 4.
The general structural formula is the chemical formula I in the summary of the invention, and the synthetic routes and principles of other compounds are the same as those of the above-mentioned examples. In examples 5 to 65 of the present application, the following luminescent auxiliary materials shown in table 1 can be obtained according to the above preparation method:
TABLE 1
Figure BDA0003687728370000311
Figure BDA0003687728370000321
Figure BDA0003687728370000331
When the organic layer includes the light-emitting auxiliary layer, the light-emitting auxiliary layer includes the light-emitting auxiliary material provided in the above embodiment.
Device example 1 preparation of Red light organic electroluminescent device
The structure of the prepared OLED device is as follows: ITO anode/HIL/HTL/luminescence auxiliary layer/EML/HBL/ETL/EIL/cathode/light extraction layer
a. An ITO anode: coating with a thickness of
Figure BDA0003687728370000341
The ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate is cleaned in distilled water for 2 times, ultrasonically cleaned for 30min, then repeatedly cleaned for 2 times by distilled water, ultrasonically cleaned for 10min, and after the cleaning is finished, ultrasonically cleaned by methanol, acetone and isopropanol in sequence (each time for 5 min), dried, then transferred into a plasma cleaning machine for cleaning for 5min, and then sent into an evaporation machine, and other functional layers are evaporated on the substrate by taking the substrate as an anode in sequence.
b. HIL (hole injection layer): to be provided with
Figure BDA0003687728370000342
The hole injection layer materials HT-1 and P-dopant were vacuum evaporated, and the chemical formulas are shown below. The evaporation rate ratio of HT-1 to P-dock is 97:3, the thickness is 10nm;
c. HTL (hole transport layer): to be provided with
Figure BDA0003687728370000343
The evaporation rate of (2), and carrying out vacuum evaporation on the hole injection layer to form 130nm HT-1 as a hole transport layer;
d. a light-emitting auxiliary layer: to be provided with
Figure BDA0003687728370000344
Vacuum evaporating 10nm of the compound 2 provided in the above example as a light-emitting auxiliary layer on the hole transport layer;
e. EML (light-emitting layer): then on the above-mentioned luminescence auxiliary layer so as to
Figure BDA0003687728370000345
The chemical formulae of Host-1 and Dopant-1 are shown below, and Host-1 and Dopant-1 are used as light-emitting layers, which are formed by vacuum evaporation of a Host material (Host-1) and a Dopant material (Dopant-1) having a thickness of 20 nm. Wherein the evaporation rate ratio of the double Host-1 to the Dopan-1 is 98:2.
f. HBL (hole blocking layer): to be provided with
Figure BDA0003687728370000346
The hole-blocking layer HB was vacuum-deposited at a thickness of 5.0 nm.
g. ETL (electron transport layer): to be provided with
Figure BDA0003687728370000351
The chemical formula of ET-1 is shown below, and ET-1 and Liq with the thickness of 35nm are vacuum evaporated to be used as electron transport layers. Wherein the evaporation rate ratio of ET-1 to Liq is 50:50.
h. EIL (electron injection layer): to be provided with
Figure BDA0003687728370000352
The evaporation rate of (2) and the evaporation of the Yb film layer is 1.0nm to form the electron injection layer.
i. Cathode: to be provided with
Figure BDA0003687728370000353
The evaporation rate ratio of (1) is that the evaporation rate ratio of magnesium to silver is 18nm, and is 1:9, so that the OLED device is obtained.
j. Light extraction layer: to be provided with
Figure BDA0003687728370000354
CPL-1 was vacuum-deposited on the cathode at a thickness of 70nm to form a light extraction layer.
K. And then packaging the evaporated substrate. Firstly, coating the cleaned cover plate by using UV glue through gluing equipment, then moving the coated cover plate to a pressing working section, placing the evaporated substrate on the upper end of the cover plate, finally, attaching the substrate and the cover plate under the action of attaching equipment, and simultaneously, finishing the illumination and solidification of the UV glue.
Figure BDA0003687728370000355
With reference to the method provided in device example 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, 119, 120, 122, 125, 126, 129, 139, 156, 183, 189, 190, 192, 212, 224, 226, 229, 230, 231, 233, 238, 274, 280, 281, 284, 285 are selected respectively instead of compound 2, and evaporation of a light-emitting auxiliary layer is performed to prepare corresponding organic electroluminescent devices, which are respectively denoted as device examples 2 to 65.
Device comparative example 1:
this comparative example provides an organic electroluminescent device whose preparation process differs from that of device example 1 only in that the organic electroluminescent device was vapor-deposited using the existing comparative compound a instead of the light-emitting auxiliary material (compound 2) in device example 1 described above. Wherein the chemical structural formula of comparative compound a is shown below.
Device comparative example 2:
this comparative example provides an organic electroluminescent device whose preparation process differs from that of device example 1 only in that the organic electroluminescent device was vapor-deposited using the existing comparative compound b instead of the light-emitting auxiliary material (compound 2) in device example 1 described above. Wherein the chemical structural formula of comparative compound b is shown below.
Device comparative example 3:
this comparative example provides an organic electroluminescent device whose preparation process differs from that of device example 1 only in that the organic electroluminescent device was vapor-deposited using the existing comparative compound c instead of the light-emitting auxiliary material (compound 2) in device example 1 described above. Wherein the chemical structural formula of comparative compound c is shown below.
Figure BDA0003687728370000371
The organic electroluminescent devices obtained in the above device examples 1 to 65 and device comparative examples 1 to 3 were characterized at a luminance of 6000 (nits) for driving voltage, luminous efficiency and lifetime, and the test results are as follows in table 2:
TABLE 2
Figure BDA0003687728370000372
Figure BDA0003687728370000381
Figure BDA0003687728370000391
As can be seen from table 2, the device performance was changed by changing the substituents and the positions of the substituents. Compared with the existing organic electroluminescent device provided by the comparative compound, the organic electroluminescent device prepared by using the luminescent auxiliary material provided by the application has the advantages that the luminous efficiency and the service life are improved.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A luminescent auxiliary material is characterized in that the structural general formula of the luminescent auxiliary material is shown in a chemical formula I:
Figure FDA0003687728360000011
x is selected from one of O, S; y is selected from the group consisting of a connecting bond, C (R) 6 ,R 7 )、O、S、NR 8 One of (1);
R 1 independently represents one of hydrogen, deuterium, halogen, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, and substituted or unsubstituted 3-to 20-membered heterocycloalkyl, wherein the heteroatom is N, O, S, si, P, se;
R 2 、R 3 independently represent hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic acid group, phosphoric acid group, boryl, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C20 cycloalkyl other than adamantyl, substituted or unsubstituted 3-to 20-membered heterocycloalkyl wherein the heteroatom is N, O, S, si, P, se, or the like; one of substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted 3-to 30-membered heteroaryl, wherein the heteroatom is N, O, S, si, P, se; wherein R is 2 、R 3 Can not be connected with each other to form a ring;
R 4 、R 5 independently represent hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic acid group, phosphoric acid group, boryl, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted 3-to 20-membered heterocycloalkyl, wherein the heteroatom is N, O, S, si, P, se; one of substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted 3-to 30-membered heteroaryl, wherein the heteroatom is N, O, S, si, P, se;
R 6 、R 7 、R 8 independently represent hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted 3-to 20-membered heterocycloalkyl, wherein the heteroatom is N, O, S, si, P, se, or the like; one of substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted 3-to 30-membered heteroaryl, wherein the heteroatom is N, O, S, si, P, se;
ar is a substituent fused on a benzene ring, and Ar may be fused at the 12-position or 34-position of the benzene ring.
Ar represents a substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 20-membered heteroaryl, the heteroatom of which is selected from O, N, S;
Ar 1 independently represent substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3-to 30-membered heterocycloalkyl, wherein the heteroatom is N, O, S, si, P, se; substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, wherein the heteroatom is N, O, S, si, P, se; a substituted or unsubstituted C10-C30 fused ring group;
Ar 2 independently represented as a dianilino group.
2. A luminescent auxiliary material as claimed in claim 1, wherein the general structural formula of the luminescent auxiliary material is one of the following structures:
Figure FDA0003687728360000021
3. luminescent support material according to claim 1 or 2, wherein Y is a bond; the R is 2 、R 3 Is hydrogen.
4. The luminescent support material of claim 1, wherein Ar is one of a substituted or unsubstituted C6-C20 aryl, a substituted or unsubstituted 3-20 membered heteroaryl, wherein the heteroatom is N, O, S, si, P, se.
5. The luminescent auxiliary material according to claim 4, wherein Ar is a phenyl group.
6. The luminescent auxiliary material according to claim 1 or 2, wherein the Ar is 1 Is one of the following structures:
Figure FDA0003687728360000031
7. a luminescent auxiliary material as claimed in claim 1 or 2, wherein the general structural formula of the luminescent auxiliary material is one of the following structures:
Figure FDA0003687728360000041
8. a luminescent auxiliary material as claimed in claim 1,2 or 7, wherein the general structural formula of the luminescent auxiliary material is one of the following structures:
Figure FDA0003687728360000051
Figure FDA0003687728360000061
Figure FDA0003687728360000071
Figure FDA0003687728360000081
Figure FDA0003687728360000091
Figure FDA0003687728360000101
Figure FDA0003687728360000111
Figure FDA0003687728360000121
Figure FDA0003687728360000131
9. a method of preparing a luminescent support material, comprising:
Figure FDA0003687728360000141
dissolving a raw material A and a raw material B in a toluene solution, adding tris (dibenzylideneacetone) dipalladium, tri-tert-butylphosphine and sodium tert-butoxide under the protection of nitrogen, uniformly stirring, and heating to reflux for reaction to obtain an intermediate 1;
dissolving the intermediate 1 and the raw material C in a toluene solution, adding tris (dibenzylideneacetone) dipalladium, tri-tert-butylphosphine and sodium tert-butoxide under the protection of nitrogen, stirring uniformly, and heating to reflux for reaction to obtain an intermediate 2;
dissolving the intermediate 2 and the raw material D in a toluene solution, adding tris (dibenzylideneacetone) dipalladium, tri-tert-butylphosphine and sodium tert-butoxide under the protection of nitrogen, stirring uniformly, and heating to reflux for reaction to obtain the luminescent auxiliary material shown in the chemical formula I.
10. A light-emitting device comprising the light-emission assisting material according to any one of claims 1 to 8 or the light-emission assisting material produced by the method for producing a light-emission assisting material according to claim 9.
CN202210658885.9A 2022-06-10 2022-06-10 Luminous auxiliary material, preparation method thereof and luminous device Pending CN115181074A (en)

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CN113307770A (en) * 2021-05-21 2021-08-27 吉林奥来德光电材料股份有限公司 Luminescent auxiliary material and preparation method and application thereof
CN113402443A (en) * 2021-05-21 2021-09-17 吉林奥来德光电材料股份有限公司 Luminescent auxiliary material containing triarylamine functional groups, preparation method thereof and organic electroluminescent device

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