CN112480114A

CN112480114A - Organic electroluminescent compound, preparation method and application thereof

Info

Publication number: CN112480114A
Application number: CN202011379782.6A
Authority: CN
Inventors: 汪康; 黄悦; 金成寿; 王永光; 贾宇; 王士凯; 马晓宇
Original assignee: Jilin Optical and Electronic Materials Co Ltd
Current assignee: Jilin Optical and Electronic Materials Co Ltd
Priority date: 2020-11-30
Filing date: 2020-11-30
Publication date: 2021-03-12

Abstract

The invention relates to the technical field of organic photoelectric materials, in particular to an organic electroluminescent compound, and a preparation method and application thereof. The organic electroluminescent compound provided by the invention has a structure shown in a formula I, and the parent nucleus is a nitrogen-containing hetero-spiro, so that the organic electroluminescent compound has very good hole transport property, very good electron blocking property and good thermal stability. Can be used as a hole transport layer material of an organic electroluminescent device. When used in an OLED, the OLED can be made to have a long lifetime, high quantum efficiency, and a low operating voltage. Experimental results show that the organic electroluminescent device prepared by taking the organic electroluminescent compound provided by the invention as a hole transport layer has higher luminous efficiency and service life and lower driving voltage.

Description

Organic electroluminescent compound, preparation method and application thereof

Technical Field

The invention relates to the technical field of organic photoelectric materials, in particular to an organic electroluminescent compound, and a preparation method and application thereof.

Background

The organic electroluminescence technology can be used for manufacturing novel display products and novel illumination products, is expected to replace the existing liquid crystal display and fluorescent lamp illumination, and has wide application prospect. The OLED light-emitting device is like a sandwich structure and comprises a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer and an electron injection layer. The Hole Transport Layer (HTL) is responsible for adjusting the injection rate and injection amount of holes, and the Electron Transport Layer (ETL) is responsible for adjusting the injection rate and injection amount of electrons.

Wherein the electron transport material should meet the requirements: (1) the electron mobility is high; (2) the cathode has higher electron affinity and is easy to inject electrons from the cathode; (3) the relatively high ionization energy is favorable for blocking holes; (4) the ability to form an exciplex with the light-emitting layer; (5) good film forming property and thermal stability, and difficult crystallization. At present, the hole mobility of a hole transport material in an existing OLED device is generally much greater than the electron mobility of an electron transport material, and such carrier transport rate imbalance can bring about significant degradation of device performance. Thus, has better electron mobility, and can effectively transport electrons to recombination regions far away from the cathode. Tris (8-hydroxyquinoline) aluminum (Alq3) has been used as an electron transport material for nearly 30 years since the invention, and there is much data to prove that it is superior to conventional materials. However, the application of the material as an electron transport material is restricted by factors such as movement to other layers.

In addition, for the collocation of OLED devices with different structures, the used photoelectric functional materials have stronger selectivity, and the performance of the same materials in the devices with different structures can also be completely different. Therefore, aiming at the industrial application requirements of the current OLED device, different functional film layers of the OLED device and the photoelectric characteristic requirements of the device, a more suitable OLED functional material or material combination with high performance needs to be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device.

Disclosure of Invention

In view of the above, the technical problem to be solved by the present invention is to provide an organic electroluminescent compound, a preparation method and an application thereof, wherein an organic electroluminescent device prepared from the organic electroluminescent compound of the present invention has high luminous efficiency and long lifetime.

The invention provides an organic electroluminescent compound, which has a structure shown in a formula I:

wherein Z is₁、Z₂、Z₃And Z₄Independently selected from the group of structures represented by formula II;

n, m, p and q are independently selected from 1 or 0, and only one of n, m, p and q may be 1 at the same time;

R₁、R₂、R₃、R₄and R₅Independently selected from hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino, sulfonic acid group, sulfonyl, phosphate group, phosphoryl, silicon group, boryl, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C3-C30 arylamino, substituted or unsubstituted C1-C30 alkoxy, or substituted or unsubstituted C6-C60 aryloxy;

or R₁、R₂、R₃、R₄And R₅Independently connect with adjacent substituent to form monocyclic ring, aliphatic ring of C3-C30 or aromatic ring of C3-C30; the carbon atom in the monocyclic ring, the aliphatic ring of C3-C30 or the aromatic ring of C3-C30 may be replaced by at least one of nitrogen, oxygen and sulfur;

Ar₁and Ar₂Independently selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaryl or substituted or unsubstituted C6-C60 arylamine;

l is selected from a connecting bond, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group.

In certain embodiments of the present invention, the organic electroluminescent compounds have the structures represented by formulas (I-1) to (I-4):

in certain embodiments of the invention, R₁、R₂、R₃、R₄And R₅Independently selected from hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino, sulfonic acid group, sulfonyl, phosphate group, phosphoryl, silicon group, boryl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C6-C18 heteroaryl, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C3-C30 arylamino, substituted or unsubstituted C1-C30 alkoxy or substituted or unsubstituted C6-C60 aryloxy.

In certain embodiments of the invention, R₁、R₂、R₃、R₄And R₅Independently connect with adjacent substituent to form monocyclic ring, aliphatic ring of C3-C20 or aromatic ring of C3-C20; the monocyclic ring is C3-C20The aliphatic ring or the aromatic ring having C3 to C20 may be substituted with at least one of nitrogen, oxygen and sulfur.

In certain embodiments of the present invention, Ar₁And Ar₂Independently selected from substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C3-C15 heterocycloalkyl, substituted or unsubstituted C6-C20 aryl or substituted or unsubstituted C6-C20 heteroaryl.

In certain embodiments of the present invention, Ar₁And Ar₂Independently selected from any one of the following structures:

in certain embodiments of the invention, L is selected from a linkage, a substituted or unsubstituted C6-C15 aryl, or a substituted or unsubstituted C3-C15 heteroaryl.

In certain embodiments of the invention, L is selected from a linkage, phenyl, deuterated phenyl, biphenyl, or naphthyl.

In the present invention, the term "substituted" means that a hydrogen atom bonded to a carbon atom of a compound becomes another substituent, and the position of substitution is not limited as long as the position is a position at which the hydrogen atom is substituted (i.e., a position at which the substituent may be substituted), and when two or more substituents are substituted, the two or more substituents may be the same as or different from each other. That is, the "substitution" in the above-mentioned "substituted or unsubstituted", may preferably be one or more of deuterium, cyano, halogen, nitro, hydroxyl, phosphate, boryl, silyl, C1-C10 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C6-C20 aryl, 3-to 10-membered heteroaryl, C1-C10 alkoxy and C6-C20 arylamino.

In some embodiments of the present invention, the organic electroluminescent compounds have the structures represented by formulas (H-001) to (H-092):

the present invention is not particularly limited to the method for preparing the above-described organic electroluminescent compounds, and in certain embodiments of the present invention, when L is not a connecting bond, the method for preparing the organic electroluminescent compounds comprises the steps of:

a) mixing a compound shown in a formula A, a compound shown in a formula B, tetrakis (triphenylphosphine) palladium and potassium carbonate, and carrying out reflux reaction to obtain an intermediate 1;

b) mixing an organic solution containing the intermediate 1 and n-butyllithium with an organic solution of a compound shown in a formula C, reacting, and obtaining an intermediate 2 after terminating the reaction;

c) mixing the intermediate 2, palladium hydroxide and sodium formate, and reacting to obtain an intermediate 3;

d1) mixing the intermediate 3, the compound shown in the formula D, tetrakis (triphenylphosphine) palladium and potassium carbonate, and then carrying out reflux reaction to obtain an intermediate 4;

e) mixing the intermediate 4, the compound shown in the formula E, a palladium catalyst, a phosphine ligand and sodium tert-butoxide, and carrying out reflux reaction to obtain an organic electroluminescent compound with a structure shown in a formula I;

l is selected from substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl;

Hal₁、Hal₂and Hal₃Independently selected from bromine or iodine.

In certain embodiments of the present invention, when L is a connecting bond, the method for preparing the organic electroluminescent compound comprises the steps of:

d2) mixing the intermediate 3, the compound shown in the formula E, a palladium catalyst, a phosphine ligand and sodium tert-butoxide, and carrying out reflux reaction to obtain an organic electroluminescent compound with a structure shown in a formula I;

R₁、R₂、R₃、R₄and R₅Independently selected from hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino, sulfonic group, sulfonyl, phosphoric group, phosphoryl, silicon base, boryl, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl,Substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C3-C30 arylamino, substituted or unsubstituted C1-C30 alkoxy or substituted or unsubstituted C6-C60 aryloxy;

l is selected from a connecting bond;

Hal₁、Hal₂and Hal₃Independently selected from bromine or iodine.

In step a):

in certain embodiments of the present invention, the reflux reaction is performed under a nitrogen blanket.

In certain embodiments of the present invention, the solvent used in the reflux reaction is a mixed solvent comprising toluene, ethanol and water. In certain embodiments, the volume ratio of toluene, ethanol, and water is 3:1: 1.

in certain embodiments of the present invention, the temperature of the reflux reaction is 90 ℃ and the time of the reflux reaction is 5 hours.

In some embodiments of the present invention, after the reflux reaction is finished, the method further includes:

cooling to room temperature, retaining the organic phase, extracting the aqueous phase with ethyl acetate, combining the organic phases, drying with anhydrous magnesium sulfate, and removing the solvent with a rotary evaporator to obtain a solid organic matter; and dissolving the solid organic matter by using dichloromethane, slowly dropwise adding the dissolved solid organic matter into a petroleum ether solution, uniformly stirring, carrying out suction filtration, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to obtain an intermediate 1.

In step b):

preferably, step b) comprises:

and (3) dropwise adding the organic solution of the compound shown in the formula C into the organic solution containing the intermediate 1 and n-butyllithium, stirring at room temperature for reaction, and stopping the reaction to obtain an intermediate 2.

In certain embodiments of the invention, the solvent in the organic solution of the compound of formula C is anhydrous diethyl ether.

In certain embodiments of the invention, the solvent in the organic solution comprising intermediate 1 and n-butyllithium is anhydrous diethyl ether.

In certain embodiments of the present invention, the dropping and the reacting are performed under a nitrogen protection.

In certain embodiments of the invention, the temperature of the dropwise addition is-78 ℃.

In certain embodiments of the invention, the reaction time is 12 hours.

In certain embodiments of the invention, the reaction is terminated by the addition of a saturated ammonium chloride solution.

In certain embodiments of the present invention, after terminating the reaction, further comprising:

extracting the reacted solution with ethyl acetate, combining organic phases, washing with water and saturated saline water in sequence, and drying with anhydrous magnesium sulfate; and dissolving the dried solid in a methanol solution, heating and stirring, carrying out suction filtration while the solid is hot, leaching the obtained solid with petroleum ether, and drying to obtain an intermediate 2.

In step c):

in certain embodiments of the present invention, the mixed feedstock further comprises a solvent para-xylene solution.

In certain embodiments of the invention, the temperature of the reaction is 140 ℃ and the time of the reaction is 24 h. In certain embodiments of the invention, the reaction is carried out under stirring.

In some embodiments of the present invention, after the reaction is finished, the method further comprises:

cooled to room temperature, extracted with dichloromethane and the resulting organic phase washed with saturated brine, dried over anhydrous sodium sulfate and dried to give intermediate 3.

In step d 1):

cooling to room temperature, retaining the organic phase, extracting the aqueous phase with ethyl acetate, combining the organic phases, drying with anhydrous magnesium sulfate, and removing the solvent with a rotary evaporator to obtain a solid organic matter; and dissolving the solid organic matter by using dichloromethane, slowly dropwise adding the dissolved solid organic matter into a petroleum ether solution, uniformly stirring, carrying out suction filtration, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to obtain an intermediate 4.

In step e):

in certain embodiments of the invention, the mixing specifically comprises:

and dissolving the intermediate 4 and the compound shown as the formula E in a toluene solution, adding a palladium catalyst, a phosphine ligand and sodium tert-butoxide, and uniformly stirring.

In certain embodiments of the invention, the palladium catalyst comprises tris (dibenzylideneacetone) dipalladium.

In certain embodiments of the invention, the phosphine ligand comprises tri-tert-butylphosphine.

In certain embodiments of the invention, the mixing and refluxing reactions are carried out under a blanket of nitrogen.

In some embodiments of the present invention, after the refluxing reaction, the method further comprises:

cooling, filtering with diatomite (the filtering process is the process of removing the catalyst and the salt), cooling the filtrate to room temperature, washing with water, retaining the organic phase, extracting the aqueous phase with ethyl acetate, combining the organic phases, drying with anhydrous magnesium sulfate, and removing the solvent with a rotary evaporator to obtain a solid organic matter; and purifying the solid organic matter by using a mixed solution of dichloromethane and petroleum ether through a chromatographic column to obtain the organic electroluminescent compound with the structure shown in the formula I.

In certain embodiments of the invention, the volume ratio of dichloromethane to petroleum ether is 10: 4.

in step d 2):

in certain embodiments of the invention, the mixing specifically comprises:

and dissolving the intermediate 3 and the compound shown in the formula E in a toluene solution, adding a palladium catalyst, a phosphine ligand and sodium tert-butoxide, and uniformly stirring.

the organic electroluminescent compound provided by the invention can be used as a hole transport layer material of an organic electroluminescent device and has higher thermal stability.

The invention also provides an organic electroluminescent device which comprises the organic electroluminescent compound or the organic electroluminescent compound prepared by the preparation method.

In some embodiments of the present invention, the organic electroluminescent device comprises a first electrode, a second electrode, and one or more layers of organic material, at least one layer of organic material comprising the organic electroluminescent compounds of the present invention.

The organic material layer of the organic electroluminescent device provided by the invention can be a single-layer structure, and can also be a multi-layer structure comprising two or more organic material layers. For example, one or more of 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, a light extraction layer, and the like can be used as the organic material layer. However, the structure of the organic 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. In some embodiments of the present invention, the organic electroluminescent device comprises, in order: an anode layer, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode layer, and a light extraction layer.

As a material of the anode layer, a material having a large work function is generally preferable so that holes are smoothly injected into the organic material layer. In some embodiments of the inventionIn the embodiment, specific examples of the anode material that can be used include: metals, such as one or more of vanadium, chromium, copper, zinc and gold, or alloys thereof; metal oxides such as one or more of zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and oxides, e.g. ZnO: Al or SnO₂Sb; conductive polymers, e.g. poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDOT), polypyrrole and polyaniline, but are not limited thereto.

In some embodiments of the invention, the material of the anode layer is indium tin oxide. In certain embodiments of the invention, the anode layer has a thickness of 150 nm.

The material of the hole injection layer is a material that advantageously receives holes from the anode at low voltages, 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 the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic material, hexanenitrile-based hexaazatriphenylene-based organic material, quinacridone-based organic material, perylene-based organic material, anthraquinone, and polyaniline-and polythiophene-based conductive polymer, and the like, but are not limited thereto, and may further include another compound capable of p-doping. In certain embodiments of the present invention, the material of the hole injection layer is HAT-CN. In some embodiments of the present invention, the hole injection layer has a thickness of 10 nm.

In the invention, the hole transport layer material comprises an organic electroluminescent compound with a structure shown in a formula I. In some embodiments of the invention, the hole transport layer has a thickness of 15 nm.

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.

In some embodiments of the present invention, the material of the light emitting layer includes a host material EMH-1 and a dopant material EMD-1, and the mass ratio of the host material to the dopant material is 97: 3. in some embodiments of the present invention, the light emitting layer has a thickness of 40 nm.

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 are not limited thereto. The thickness of the electron transport layer may be 1nm to 50 nm. 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.

In certain embodiments of the present invention, the material of the electron transport layer comprises ET-1 and Liq, the mass ratio of ET-1 to Liq being 60: 40. in certain embodiments of the present invention, the electron transport layer has a thickness of 35 nm.

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.

In certain embodiments of the present invention, the material of the electron injection layer is Yb (ytterbium). In some embodiments of the present invention, the electron injection layer has a thickness of 1 nm.

As a material of the cathode layer, a material having a small work function is generally preferable 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 LiO 2/Al; and the like, but are not limited thereto.

In certain embodiments of the present invention, the material of the cathode layer comprises magnesium and silver, the mass ratio of magnesium to silver being 1: 9. in certain embodiments of the invention, the cathode layer has a thickness of 70 nm.

The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.

The organic electroluminescent device provided by the invention can be applied to Organic Light Emitting Devices (OLEDs), Organic Solar Cells (OSCs), electronic paper (e-paper), Organic Photoreceptors (OPC) or Organic Thin Film Transistors (OTFTs).

The organic electroluminescent compound provided by the invention has a structure shown in a formula I, and the parent nucleus is a nitrogen-containing hetero-spiro, so that the organic electroluminescent compound has very good hole transport property, very good electron blocking property and good thermal stability. Can be used as a hole transport layer material of an organic electroluminescent device. When used in an OLED, the OLED can be made to have a long lifetime, high quantum efficiency, and a low operating voltage. Experimental results show that the organic electroluminescent device prepared by taking the organic electroluminescent compound provided by the invention as a hole transport layer has higher luminous efficiency and service life and lower driving voltage.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

Synthesis of Compound H-013:

1. raw material A-013(11.52g, 50.00mmol) and raw material B-013(10.04g, 50.00mmol) were dissolved in 200.00mL of toluene, ethanol and water (V)_Toluene:V_Ethanol:V_{Water (W)}3:1:1), then replacing air with nitrogen for 3 times, adding tetratriphenylphosphine palladium (0.58g, 0.5mmol) and potassium carbonate (13.82g, 100.00mmol) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, refluxing for 5 hours, after the solution is cooled to room temperature, retaining an organic phase, and then extracting an aqueous phase with ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. 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 100.00mL of absolute ethyl alcohol and 100.00mL of petroleum ether, and drying to obtain an intermediate 1-013(12.98g, yield: 84.66%);

2. intermediate 1-013(12.00g, 39.14mmol) was dissolved in 120.00ml of anhydrous ether under nitrogen to give mixed solution 1. The mixed solution 1 was cooled to-78 ℃ and stirred for 10min, followed by dropwise addition of n-BuLi (4.01g, 62.62mmol), and the reaction was continued with stirring for 1 hour. Raw material C-013(7.05g, 39.14mmol) was dissolved in 70.00mL of anhydrous ether solution to give mixed solution 2. Under the protection of nitrogen, the mixed solution 2 was slowly added dropwise to the above reaction system, and after stirring at-78 ℃ for 10min, it was transferred to room temperature and stirred for 12 h. Then, adding a saturated ammonium chloride solution to perform an extraction quenching reaction, extracting the reaction solution for 3 times by using ethyl acetate, combining organic phases, washing the organic phases by using water and saturated saline water successively, drying the organic phases by using anhydrous magnesium sulfate, dissolving the solid obtained by drying in 120.00mL of methanol solution, heating and stirring the solution for 5 hours, performing suction filtration on the solution while the solution is hot to obtain a solid, leaching the solid by using petroleum ether, and drying the solid to prepare an intermediate 2-013(13.85g, yield: 86.72%);

3. under the protection of nitrogen, dissolving the intermediate 2-013(13.00g, 31.87mmol), palladium hydroxide (0.45g, 3.19mmol) and sodium formate (1.08g, 15.94mmol) in 150.00mL of p-xylene solution, heating to 140 ℃ in an oil bath, stirring for 24h, extracting with dichloromethane for 3 times after the solution is cooled to room temperature, then combining organic phases, washing with saturated saline solution, drying with anhydrous sodium sulfate, dissolving the solid organic matter in 150.00mL of toluene solution, heating and stirring for 5h, filtering the solution to obtain a solid after the solution is cooled to room temperature, then leaching with petroleum ether, and drying to prepare the intermediate 3-013(9.51g, yield: 76.51%);

4. intermediate 3-013(9.00g, 23.08mmol) and starting material E-013(5.71g, 23.08mmol) were dissolved in 150.00mL of toluene solution, followed by replacement of air with nitrogen 3 times, and tris (dibenzylideneacetone) dipalladium (0.21g, 0.23mmol), tri-tert-butylphosphine (0.23g, 0.23mmol) were added under nitrogeng, 1.15mmol) and sodium tert-butoxide (4.44g, 46.16mmol), 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; using methylene chloride and petroleum ether (V)_{Methylene dichloride}:V_{Petroleum ether}10:4), the remaining material was purified by column chromatography to obtain compound H-013(11.44g, yield: 82.47%, Mw: 600.75).

The detection analysis of the obtained compound H-013 is as follows:

HPLC purity: is more than 99 percent.

Mass spectrometry test: a theoretical value of 600.77; the test value was 600.75.

Elemental analysis:

the calculated values are: c, 89.97; h, 5.37; and N, 4.66.

The test values are: c, 89.98; h, 5.38; and N, 4.64.

Example 2

Synthesis of Compound H-050:

1. raw material A-050(13.63g, 50.00mmol) and raw material B-050(10.74g, 50.00mmol) were dissolved in 250.00mL of toluene, ethanol, and water (V)_Toluene:V_Ethanol:V_{Water (W)}3:1:1), then replacing air with nitrogen for 3 times, adding tetratriphenylphosphine palladium (0.58g, 0.50mmol) and potassium carbonate (13.82g, 100.00mmol) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, refluxing for 5 hours, after the solution is cooled to room temperature, retaining an organic phase, and then extracting an aqueous phase with ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. The solid organics were completely dissolved using a small amount of dichloromethane and then added slowly dropwise to the stoneStirring the mixture evenly in an oil ether solution, separating out a precipitate, filtering the precipitate to obtain a solid, leaching the solid with 100.00mL of absolute ethyl alcohol and 100.00mL of petroleum ether in sequence, and drying the leached solid to obtain an intermediate 1-050(15.43g, yield: 85.11%);

2. intermediate 1-050(15.00g, 41.36mmol) was dissolved in 150.00mL of anhydrous ether solution under nitrogen to give mixed solution 1. The mixed solution 1 was cooled to-78 ℃ and stirred for 10min, followed by dropwise addition of n-BuLi (4.24g, 66.18mmol), and the reaction was continued for 1 hour with stirring. Raw material C-050(13.79g, 41.36mmol) was dissolved in 130.00mL of an anhydrous ether solution to obtain a mixed solution 2. Under the protection of nitrogen, the mixed solution 2 was slowly added dropwise to the above reaction system, and after stirring at-78 ℃ for 10min, it was transferred to room temperature and stirred for 12 h. Then, adding a saturated ammonium chloride solution for extraction and quenching reaction, extracting the reaction solution for 3 times by using ethyl acetate, combining organic phases, washing by using water and brine successively, drying by using anhydrous magnesium sulfate, dissolving the dried solid in 150.00mL of methanol solution, heating and stirring for 5 hours, carrying out suction filtration on the solution while the solution is hot to obtain a solid, leaching by using petroleum ether, and drying to prepare an intermediate 2-050(21.95g, yield: 85.97%);

3. under the protection of nitrogen, dissolving intermediate 2-050(21.00g, 34.03mmol), palladium hydroxide (0.47g, 3.40mmol) and sodium formate (1.16g, 17.02mmol) in 230.00mL of p-xylene solution, heating to 140 ℃ in an oil bath, stirring for 24h, extracting with dichloromethane for 3 times after the solution is cooled to room temperature, then combining organic phases, washing with saturated saline solution, drying with anhydrous sodium sulfate, dissolving a solid organic matter in 150.00mL of toluene solution, heating and stirring for 5h, filtering the solution to obtain a solid after the solution is cooled to room temperature, then leaching with petroleum ether, and drying to prepare intermediate 3-050(15.55g, yield: 76.24%);

4. dissolving intermediate 3-050(15.00g and 25.03mmol) and raw material E-050(8.80g and 25.03mmol) in 250.00mL of toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.23g and 0.25mmol), tri-tert-butylphosphine (0.25g and 1.26mmol) and sodium tert-butoxide (4.81g and 50.06mmol) 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; using methylene chloride and petroleum ether (V)_{Methylene dichloride}:V_{Petroleum ether}10:4), the remaining material was purified by column chromatography to obtain compound H-050(18.90g, yield: 82.61%, Mw: 914.18).

The compound H-050 thus obtained was analyzed and found to have the following results:

HPLC purity: is more than 99 percent.

Mass spectrometry test: a theoretical value of 914.18; the test value was 914.19.

Elemental analysis:

the calculated values are: c, 86.71; h, 5.18; n, 4.60; s, 3.51.

The test values are: c, 86.70; h, 5.19; n, 4.59; and S, 3.52.

Example 3

Synthesis of Compound H-061:

1. raw material A-061(15.33g, 50.00mmol) and raw material B-061(10.04g, 50.00mmol) were dissolved in 250.00mL of toluene, ethanol and water (V)_Toluene:V_Ethanol:V_{Water (W)}3:1:1), then replacing air with nitrogen for 3 times, adding tetratriphenylphosphine palladium (0.58g, 0.5mmol) and potassium carbonate (13.82g, 100.00mmol) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, refluxing for 5 hours, after the solution is cooled to room temperature, retaining an organic phase, and then extracting an aqueous phase with ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. 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 100.00mL of absolute ethyl alcohol and 100.00mL of petroleum ether, and drying to obtain an intermediate 1-061(16.21g, yield: 84.73%);

2. intermediate 1-061(16.00g, 41.81mmol) was dissolved in 160mL of anhydrous ether under nitrogen to give mixed solution 1. The mixed solution 1 was cooled to-78 ℃ and stirred for 10min, followed by dropwise addition of n-BuLi (4.29g, 66.90mmol), and the reaction was continued with stirring for 1 hour. Raw material C-061(7.53g, 41.81mmol) was dissolved in 70.00mL of anhydrous ether solution to obtain a mixed solution 2. Under the protection of nitrogen, the mixed solution 2 was slowly added dropwise to the above reaction system, and after stirring at-78 ℃ for 10min, it was transferred to room temperature and stirred for 12 h. Then, adding a saturated ammonium chloride solution for extraction and quenching reaction, extracting the reaction solution for 3 times by using ethyl acetate, combining organic phases, washing by using water and brine successively, drying by using anhydrous magnesium sulfate, dissolving the solid obtained by drying in 120.00mL of methanol solution, heating and stirring for 5 hours, carrying out suction filtration on the solution while the solution is hot to obtain a solid, leaching by using petroleum ether, and drying to prepare an intermediate 2-061(19.48 yield: 86.37%);

3. under the protection of nitrogen, dissolving the intermediate 2-061(19.00g, 39.26mmol), palladium hydroxide (0.55g, 3.93mmol) and sodium formate (1.34g, 19.63mmol) in 200.00mL of p-xylene solution, heating to 140 ℃ in an oil bath, stirring for 24 hours, extracting with dichloromethane for 3 times after the solution is cooled to room temperature, then combining organic phases, washing with saturated saline solution, drying with anhydrous sodium sulfate, dissolving the solid organic matter in 150.00mL of toluene solution, heating and stirring for 5 hours, filtering the solution to obtain a solid after the solution is cooled to room temperature, then leaching with petroleum ether, and drying to prepare the intermediate 3-061(13.97g, yield: 76.39%);

4. dissolving the intermediate 3-061(13.00g, 27.90mmol) and the raw material E-061(13.05g, 27.90mmol) in 260.00mL of toluene solution, then replacing air with nitrogen for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.26g, 0.28mmol), tri-tert-butylphosphine (0.28g, 1.40mmol) and sodium tert-butoxide (5.36g, 55.8mmol) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, and refluxing 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; using methylene chloride and petroleum ether (V)_{Methylene dichloride}:V_{Petroleum ether}10:4), and the remaining substance was purified by column chromatography to obtain compound H-061(20.78g, yield: 83.04%, Mw: 897.12).

The compound H-061 obtained was analyzed and found to have the following results:

HPLC purity: is more than 99 percent.

Mass spectrometry test: a theoretical value of 897.15; the test value was 897.12.

Elemental analysis:

the calculated values are: c, 88.36; h, 4.94; n, 3.12; and S, 3.57.

The test values are: c, 88.37; h, 4.93; n, 3.13; and S, 3.56.

Example 4

Synthesis of Compound H-072:

1. starting materials A-072(11.52g, 50.00mmol) and B-072(10.04g, 50.00mmol) were dissolved in 220.00mL of toluene, ethanol and water (V)_Toluene:V_Ethanol:V_{Water (W)}3:1:1), then replacing air with nitrogen for 3 times, adding tetratriphenylphosphine palladium (0.58g, 0.5mmol) and potassium carbonate (13.82g, 100.00mmol) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, refluxing for 5 hours, after the solution is cooled to room temperature, retaining an organic phase, and then extracting an aqueous phase with ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. 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 100.00mL of absolute ethyl alcohol and 100.00mL of petroleum ether, and drying to obtain an intermediate 1-072(15.33g, yield: 85.11%);

2. intermediate 1-072(15.00g, 48.93mmol) was dissolved in 150.00mL of anhydrous ether under nitrogen to give mixed solution 1. The mixed solution 1 was cooled to-78 ℃ and stirred for 10min, followed by dropwise addition of n-BuLi (5.02g, 78.29mmol), and the reaction was continued for 1 hour with stirring. Raw material C-072(8.82g, 48.93mmol) was dissolved in 90.00mL of anhydrous ether solution to give mixed solution 2. Under the protection of nitrogen, the mixed solution 2 was slowly added dropwise to the above reaction system, and after stirring at-78 ℃ for 10min, it was transferred to room temperature and stirred for 12 h. Then, adding saturated ammonium chloride solution to perform extraction and quenching reaction, extracting the reaction solution for 3 times by using ethyl acetate, combining organic phases, washing by using water and brine successively, drying by using anhydrous magnesium sulfate, dissolving the solid obtained by drying in 120.00mL of methanol solution, heating and stirring for 5 hours, performing suction filtration on the solution while the solution is hot to obtain a solid, leaching by using petroleum ether, and drying to prepare an intermediate 2-072(17.28g, yield: 86.55%);

3. under the protection of nitrogen, dissolving an intermediate 2-072(17.00g, 41.68mmol), palladium hydroxide (0.59g, 4.17mmol) and sodium formate (1.42g, 20.84mmol) in a p-190.00 mL xylene solution, heating to 140 ℃ in an oil bath, stirring for 24h, extracting for 3 times by dichloromethane after the solution is cooled to room temperature, then combining organic phases, washing by saturated saline solution, drying by anhydrous sodium sulfate, dissolving a solid organic matter in 150.00mL toluene solution, heating and stirring for 5h, filtering the solution to obtain a solid after the solution is cooled to room temperature, then leaching by petroleum ether, and drying to prepare an intermediate 3-072(12.32g, yield: 75.84%);

4. intermediate 3-072(12.00g, 30.78mmol) and starting material D-072(7.72g, 30.78mmol) were dissolved in 200.00mL of toluene, ethanol and water (V)_Toluene:V_Ethanol:V_{Water (W)}3:1:1), then replacing air with nitrogen for 3 times, adding tetratriphenylphosphine palladium (0.36g, 0.31mmol) and potassium carbonate (8.51g, 61.56mmol) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, refluxing for 5 hours, after the solution is cooled to room temperature, retaining an organic phase, and then extracting an aqueous phase with ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Dissolving the solid organic matter completely with a small amount of dichloromethane, slowly dripping into petroleum ether solution, stirring, precipitating, vacuum filtering to obtain solid, sequentially adding 100.00mL of anhydrous ethanol and 100.00mL ofEluting with petroleum ether, and drying to obtain intermediate 4-072(12.20g, yield: 82.32%);

5. dissolving intermediate 4-072(12.00g, 24.92mmol) and raw material E-072(9.36g, 24.92mmol) in 220.00mL of toluene solution, then replacing air with nitrogen for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.23g, 0.25mmol), tri-tert-butylphosphine (0.25g, 1.25mmol) and sodium tert-butoxide (4.79g, 49.84mmol) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, and refluxing for 5 h; 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; using methylene chloride and petroleum ether (V)_{Methylene dichloride}:V_{Petroleum ether}10:4), the remaining material was purified by column chromatography to obtain compound H-072(17.70g, yield: 83.07%, Mw: 855.04).

The compound H-072 obtained was subjected to detection analysis, and the results were as follows:

HPLC purity: is more than 99 percent.

Mass spectrometry test: a theoretical value of 855.05; the test value was 855.04.

Elemental analysis:

the calculated values are: c, 89.90; h, 4.95; n, 3.28; o, 1.87.

The test values are: c, 89.91; h, 4.96; n, 3.27; o, 1.86.

Example 5

Synthesis of Compound H-080:

1. starting materials A-080(15.33g, 50.00mmol) and B-080(10.04g, 50.00mmol) were dissolved in 250.00mL of toluene, ethanol and water (V)_Toluene:V_Ethanol:V_{Water (W)}3:1:1), then replacing air with nitrogen for 3 times, adding tetratriphenylphosphine palladium (0.58g, 0.5mmol) and potassium carbonate (13.82g, 100.00mL) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, refluxing for 5 hours, after the solution is cooled to room temperature, retaining an organic phase, and then extracting an aqueous phase with ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. 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 100.00mL of absolute ethyl alcohol and 100.00mL of petroleum ether, and drying to obtain an intermediate 1-080(16.29g, yield: 85.18%);

2. intermediate 1-080(16.00g, 41.81mmol) was dissolved in 160.00mL of anhydrous ether solution under nitrogen protection to obtain mixed solution 1. The mixed solution 1 was cooled to-78 ℃ and stirred for 10min, followed by dropwise addition of n-BuLi (4.29g, 66.90mmol), and the reaction was continued with stirring for 1 hour. Raw material C-080(13.90g, 41.81mmol) was dissolved in 140.00mL of anhydrous ether solution to obtain mixed solution 2. Under the protection of nitrogen, the mixed solution 2 was slowly added dropwise to the above reaction system, and after stirring at-78 ℃ for 10min, it was transferred to room temperature and stirred for 12 h. Then, adding a saturated ammonium chloride solution to perform extraction and quenching reaction, extracting the reaction solution for 3 times by using ethyl acetate, combining organic phases, washing by using water and brine successively, drying by using anhydrous magnesium sulfate, dissolving the solid obtained by drying in 120.00ml of methanol solution, heating and stirring for 5 hours, performing suction filtration on the solution while the solution is hot to obtain a solid, leaching by using petroleum ether, and drying to prepare an intermediate 2-080(20.29g, yield: 76.27%);

3. under the protection of nitrogen, dissolving intermediate 2-080(20.00g, 31.44mmol), palladium hydroxide (0.44g, 3.14mmol) and sodium formate (1.07g, 15.72mmol) in 210.00mL p-xylene solution, heating to 140 ℃ in an oil bath, stirring for 24h, extracting with dichloromethane for 3 times after the solution is cooled to room temperature, then combining organic phases, washing with saturated saline solution, drying with anhydrous sodium sulfate, dissolving the solid organic matter in 100.00mL toluene solution, heating and stirring for 5h, filtering the solution to obtain a solid after the solution is cooled to room temperature, then leaching with petroleum ether, and drying to prepare intermediate 3-080(14.87g, yield: 76.49%);

4. dissolving intermediate 3-080(14.00g, 22.65mmol) and raw material D-080(6.27g, 22.65mmol) in 200.00mL of a mixed solution of toluene, ethanol and water (V toluene: V ethanol: V water ═ 3:1:1), then replacing air with nitrogen for 3 times, adding palladium tetratriphenylphosphine (0.27g, 0.23mmol) and potassium carbonate (6.26g, 45.3mmol) under the protection of nitrogen, stirring uniformly, heating to 90 ℃, refluxing for 5 hours, after the solution is cooled to room temperature, retaining an organic phase, and then extracting an aqueous phase with ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. 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 100.00mL of absolute ethyl alcohol and 100.00mL of petroleum ether, and drying to prepare an intermediate 4-080(11.07g, yield: 83.04%);

5. intermediate 4-080(11.00g, 18.69mmol) and E-080(5.11g, 18.69mmol) were dissolved in 160.00mL of toluene solution, followed by displacement of air with nitrogen 3 times and addition of tris (dibenzylideneacetone) under nitrogen protectionDipalladium (0.17g, 0.19mmol), tri-tert-butylphosphine (0.19g, 0.93mmol) and sodium tert-butoxide (3.59g, 37.38mmol), stirring, heating to 90 deg.C, and refluxing for 5 h; 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; using methylene chloride and petroleum ether (V)_{Methylene dichloride}:V_{Petroleum ether}10:4), the remaining material was purified by column chromatography to obtain compound H-080(15.76g, yield: 83.71%, Mw: 1007.22).

The detection analysis of the obtained compound H-080 showed the following results:

HPLC purity: is more than 99 percent.

Mass spectrometry test: a theoretical value of 1007.25; the test value was 1007.22.

Elemental analysis:

the calculated values are: c, 90.63; h, 5.00; n, 2.78; o, 1.59.

The test values are: c, 90.64; h, 5.01; n, 2.77; o, 1.58.

Examples 6 to 15

The organic electroluminescent compounds in the following examples were synthesized according to the same synthetic route as the above examples, and the structures, yields, theoretical values of mass spectrometry, and test values of the organic electroluminescent compounds are shown in table 1.

TABLE 1 structures, yields, theoretical values and test values of mass spectrometry of organic electroluminescent compounds synthesized in examples 6 to 15

The glass transition temperatures (tg) of the compounds synthesized in examples 1 to 15 were measured using TMA4000, as shown in Table 2.

TABLE 2 glass transition temperatures of organic electroluminescent compounds synthesized in examples 1 to 15

As can be seen from Table 2, the organic electroluminescent compounds provided by the present invention have high thermal stability.

Example 16

Preparation of organic electroluminescent device:

the ITO glass substrate with the coating thickness of 150nm is placed in distilled water for cleaning for 2 times, ultrasonic cleaning is carried out for 30 minutes, the ITO glass substrate is repeatedly cleaned for 2 times by the distilled water, the ultrasonic cleaning is carried out for 10 minutes, after the cleaning by the distilled water is finished, solvents such as isopropanol, acetone, methanol and the like are sequentially subjected to ultrasonic cleaning and then dried, the ITO glass substrate is transferred into a plasma cleaning machine, the ITO glass substrate is cleaned for 5 minutes, and the ITO glass substrate is sent into an evaporation machine.

Firstly, evaporating a hole injection layer material HAT-CN on an ITO anode layer in a vacuum evaporation mode, wherein the thickness of the hole injection layer material HAT-CN is 10 nm; vacuum evaporation of 15nm of the compound H-004 provided in example 1 above on top of the hole injection layer as a hole transport layer; then, a main material EMH-1 and a doping material EMD-1 with the thickness of 40nm are subjected to vacuum evaporation on the hole transport layer to serve as a light emitting layer, wherein the weight ratio of the main material to the doping material is 97:3, and the structural formulas of the main material EMH-1 and the doping material EMD-1 are as follows; then, performing vacuum evaporation on the light-emitting layer to form ET-1 and Liq with the thickness of 35nm as an electron transport layer, wherein the weight ratio of the ET-1 to the Liq is 60:40, and the structural formula of ETH is as follows; vacuum evaporating Yb with the thickness of 1nm on the electron transport layer to form an electron injection layer; finally, performing vacuum evaporation on the electron injection layer to form magnesium and silver as cathodes, wherein the weight ratio of the magnesium to the silver is 1:9, and the evaporation thickness is 18 nm; and (3) performing vacuum evaporation on the cathode to obtain IDX001 with the thickness of 70nm as a light extraction layer, thus obtaining the organic electroluminescent device.

The molecular structural formula of the related material is shown as follows:

by referring to the method provided in device example 16 above, compounds H-013, H-018, H-023, H-032, H-038, H-043, H-050, H-057, H-061, H-069, H-072, H-074, H-077, and H-080 were selected respectively to replace compound H-004, and evaporation of the hole transport layer was performed, and corresponding organic electroluminescent devices were prepared, which were respectively identified as examples 17 to 30.

Comparative example 1

This comparative example provides an organic electroluminescent device which is produced by a method different from that of example 16 only in that the organic electroluminescent device is vapor-deposited by using a conventional compound represented by formula iii instead of the hole transport material (compound H-004) in example 1 of the above-mentioned device. Wherein, the chemical structural formula of the compound shown in the formula III is shown as follows:

the organic electroluminescent devices prepared in examples 16 to 30 and comparative example 1 were each subjected to a forward DC bias voltage, and the organic electroluminescent characteristics were measured by a PR-650 photometric measuring instrument of Photo Research, and the lifetime at T95 was measured at a luminance of 15000(nits) by a lifetime measuring apparatus of McScience. The results are shown in Table 3.

TABLE 3 test results of light emitting characteristics of organic electroluminescent devices obtained in examples 16 to 30 and comparative example 1

As can be seen from table 3, the organic electroluminescent device prepared by using the organic electroluminescent compound provided by the present invention as a hole transport layer has significantly improved luminous efficiency and lifetime and significantly reduced driving voltage, compared to the organic electroluminescent device prepared by using the comparative compound (the compound represented by formula iii) as a hole transport layer.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. 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 invention. Thus, the present invention 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

1. An organic electroluminescent compound having the structure shown in formula I:

2. The organic electroluminescent compound according to claim 1, wherein R is₁、R₂、R₃、R₄And R₅Independently selected from hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino, sulfonic acid group, sulfonyl, phosphate group, phosphoryl, silicon group, boryl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C6-C18 heteroaryl, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C3-C30 arylamino, substituted or unsubstituted C1-C30 alkoxy, or substituted or unsubstituted C6-C60 aryloxy;

or R₁、R₂、R₃、R₄And R₅Independently connect with adjacent substituent to form monocyclic ring, aliphatic ring of C3-C20 or aromatic ring of C3-C20; the monocyclic ring, the aliphatic ring of C3-C20 or C3 ℃The carbon atom in the aromatic ring of C20 may be replaced with at least one of nitrogen, oxygen, and sulfur.

3. The organic electroluminescent compound according to claim 1, wherein Ar is Ar₁And Ar₂Independently selected from substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C3-C15 heterocycloalkyl, substituted or unsubstituted C6-C20 aryl or substituted or unsubstituted C6-C20 heteroaryl.

4. The organic electroluminescent compound according to claim 1, wherein Ar is Ar₁And Ar₂Independently selected from any one of the following structures:

5. the organic electroluminescent compound of claim 1, wherein L is selected from the group consisting of a bond, a substituted or unsubstituted C6-C15 aryl, and a substituted or unsubstituted C3-C15 heteroaryl.

6. The organic electroluminescent compound according to claim 1, wherein L is selected from a connecting bond, phenyl, deuterated phenyl, biphenyl, or naphthyl.

7. The organic electroluminescent compound according to claim 1, wherein the organic electroluminescent compound has a structure represented by formula (H-001) to formula (H-092):

8. a method for preparing an organic electroluminescent compound, comprising the steps of:

Hal₁、Hal₂and Hal₃Independently selected from bromine or iodine.

9. A method for preparing an organic electroluminescent compound, comprising the steps of:

R₁、R₂、R₃、R₄and R₅Independently selected from hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino, sulfonic group, sulfonyl, phosphate group, phosphoryl, silicon base, boryl, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroarylArylamine, substituted or unsubstituted C3-C30 arylamine, substituted or unsubstituted C1-C30 alkoxy or substituted or unsubstituted C6-C60 aryloxy;

l is selected from a connecting bond;

Hal₁、Hal₂and Hal₃Independently selected from bromine or iodine.

10. An organic electroluminescent device comprising the organic electroluminescent compound according to any one of claims 1 to 7 or the organic electroluminescent compound produced by the production method according to any one of claims 8 to 9.