WO2020073605A1 - Organic luminescent compound, preparation method therefor and organic electroluminescent device containing same - Google Patents

Abstract

The present disclosure relates to the technical field of organic luminescent materials, in particular to an organic luminescent compound, a preparation method therefor and an organic electroluminescent device containing same. The present disclosure proposes a solution to introduce an arylamine and a heterocyclic ring to the 9-position of fluorene. A hole injection capability/transmission capability, a high power efficiency and a long service life are obtained by introducing an arylamine. An appropriate glass transition temperature is obtained by introducing a heterocyclic ring, thereby obtaining a high-quality organic electroluminescent material. The organic electroluminescent device prepared from the organic luminescent compound of the present disclosure has excellent current efficiency and power efficiency, and a long service life. The preparation method for the organic luminescent compound of the present disclosure has good repeatability and a high yield.

Description

Organic light-emitting compound, preparation method and organic electroluminescent device containing the compound

Cross-reference of related applications

This application requires the priority of the Chinese patent application with the application number 201910184076.7, titled "An Organic Light-Emitting Compound and its Manufacturing Method and Organic Electroluminescent Device of the Compound", filed on March 12, 2019 in the Chinese Patent Office, and The priority of the Chinese patent application with the application number 201811180929.1 and the title of "an organic light-emitting compound and its preparation method and organic electroluminescent device containing the compound" filed on October 11, 2018 with the Chinese Patent Office Incorporated by reference in this application.

Technical field

The present disclosure relates to the technical field of organic light-emitting materials, in particular to an organic light-emitting compound, a preparation method, and an organic electroluminescent device of the compound.

Background technique

An electroluminescence device (EL device) is an automatic light-emitting device, which has the advantage that it can provide a wider viewing angle, a larger contrast ratio, and a faster response time.

An organic EL element is a self-luminous element that utilizes the principle that by applying an electric field, the recombination of holes injected from the anode and electrons injected from the cathode can cause the fluorescent substance to emit light. It has the following structure: anode, cathode and organic layer between them. In order to improve the efficiency and stability of the organic EL element, the organic material layer includes multiple layers with different materials, such as a hole injection layer (HIL), a hole transport layer (HTL), a light emitting layer, an electron transport layer (ETL), and electrons Injection layer (EIL).

In such an organic light emitting diode, when a voltage is applied between the anode and the cathode, holes from the anode and electrons from the cathode are injected into the organic material layer. The generated excitons generate light with a specific wavelength when they migrate to the ground state.

The most important factor that determines the luminous efficiency in organic EL devices is the luminescent material. So far, fluorescent materials have been widely used as light-emitting materials. However, in view of the electroluminescence mechanism, since the phosphorescent material theoretically enhances the luminous efficiency by four (4) times compared with the fluorescent material, the development of the phosphorescent light-emitting material has been extensively studied. Iridium (III) complexes have been widely referred to as phosphorescent doping materials. Currently, 4,4'-N, N'-dicarbazole-biphenyl (CBP), 9,10-bis (2-naphthyl) anthracene (ADN), etc. are widely used as known phosphorescent host materials. Although these materials provide good luminescence characteristics, they have the following disadvantages: (1) Due to their lower glass transition temperature and poor thermal stability, the life of the device is reduced. (2) Organic EL devices containing phosphorescent host materials require higher driving voltages. Meanwhile, in order to improve the efficiency and stability of the organic EL device, it is required to have a multilayer structure including 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 can change the hole transport efficiency from the hole to the light emitting layer, luminous efficiency, life, etc. Therefore, copper phthalocyanine (CuPc), 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB), N, N'-diphenyl-N, N '-Bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine (TPD) etc. are used as hole transport materials. However, organic EL devices using these materials have problems in quantum efficiency and service life.

Summary of the invention

The present disclosure provides an organic light emitting compound, the structural formula of which is as follows:

In the formula: Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, or a substituted or unsubstituted 3-30 membered heteroaryl; or connected with adjacent substituents to form a monocyclic or C ₃ -C ₃₀ polycyclic alicyclic ring or aromatic ring, the carbon atom of which can be replaced by at least one selected from nitrogen, oxygen and sulfur Of heteroatoms;

Ring G represents a substituted or unsubstituted C ₁ -C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, or a substituted or unsubstituted 3-30 membered heteroaryl group;

The G ring may or may not exist;

When G ring does not exist, X, Y, Z represent -O-, -S-, -SO _2- , -C (R ₅ ) (R ₆ )-, -N (R ₇ )-, -Si (R ₅ ) (R ₆ )-, -Sn (R ₇ )-or -Ge (R ₇ )-;

When the G ring exists, X represents -SO _2- , -N (R ₇ )-, -Si (R ₅ ) (R ₆ )-, Sn (R ₇ )-, or -Ge (R ₇ )-; Y, Z represent C, N, O, S atoms; G ring is preferably benzene ring, naphthalene ring, pyridine ring, 1-phenyl-1H-indole, benzofuran, benzothiophene, 4-phenyl-4H-benzo [b ] [1,4] oxazine, 4-phenyl-4H-benzothiazine, benzothiophene, 1,4-diphenyl-1,4-dihydroquinoxaline or 1,1,4,4 -Tetramethyl-1,4-dihydronaphthalene;

R ₁ to R ₄ each independently represent hydrogen, deuterium, halogen, cyano, carboxy, nitro, hydroxyl, substituted or unsubstituted C ₁ -C ₃₀ hydrocarbons, substituted or unsubstituted C _1- C ₃₀ alkoxy, substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl, substituted or unsubstituted C ₃ -C ₃₀ cycloalkenyl, substituted or unsubstituted 3-7 membered hetero Cycloalkyl, substituted or unsubstituted C ₆ -C ₃₀ aryl, substituted or unsubstituted 3-30 membered heteroaryl, -NR ₈ R ₉ , -SiR ₁₀ R ₁₁ R ₁₂ , -SR ₁₃ , -OR ₁₄ , -COR ₁₅ or -B (OR ₁₆ ) (OR ₁₇ ); or connected with adjacent substituents to form a substituted or unsubstituted monocyclic ring or C ₃ -C ₃₀ polycyclic aliphatic ring or Aromatic ring, its carbon atom can be replaced with at least one heteroatom selected from nitrogen, oxygen and sulfur;

R ₅ to R ₁₇ each independently represent hydrogen, a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, or a substituted or unsubstituted 3 Up to 30-membered heteroaryl; or linked to adjacent substituents to form substituted or unsubstituted monocyclic or C ₃ -C ₃₀ polycyclic aliphatic or aromatic rings;

a, b, and d independently represent integers 1 to 4; c represents integers 1 to 3.

The present disclosure also provides a method for preparing an organic light-emitting compound, including the following steps:

Step 1. After adding Compound 2 and tetrahydrofuran to the reaction vessel, the vessel was cooled to -78 ° C under a nitrogen atmosphere, then n-butyllithium was added dropwise to the mixture, and after stirring the mixture at -78 ° C, It was stirred at room temperature and cooled to -78 ° C; thereafter, Compound 1 dissolved in tetrahydrofuran was added dropwise to the mixture; after the addition, the reaction temperature was raised to room temperature, and the mixture was stirred; then the chlorination An aqueous ammonium solution was added to the reaction solution to complete the reaction, and the reaction solution was extracted with ethyl acetate, followed by drying the extracted organic layer with magnesium sulfate, and the solvent was removed using a rotary evaporator, and the remaining material was purified by column chromatography to obtain an intermediate Body 1-1;

Step 2. After adding Intermediate 1-1, Compound 3 and methylene chloride to the reaction vessel, fully replace the air with nitrogen three times, and add boron trifluoride ether dissolved in methylene chloride dropwise to the mixture; After stirring the mixture at room temperature, it was quenched with distilled water, and the mixture was extracted with dichloromethane; then the extracted organic layer was dried using sodium sulfate, and the solvent was removed using a rotary evaporator, and the remaining material was purified by column chromatography to obtain intermediate 2;

Step 3. Intermediate 2, Ar ₁ Br and Ar ₂ Br, Pd ₂ (dba) ₃ , P (t-Bu) ₃ , NaOt-Bu, toluene are reacted; after the reaction is completed, the organic matter is extracted with ether and water. The concentrated product after the layer was dried with magnesium sulfate was used to obtain the compound of formula 1 by silica gel column and recrystallization method;

The synthetic route is as follows:

In the formula: Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, or a substituted or unsubstituted 3-30 membered heteroaryl; or connected with adjacent substituents to form a monocyclic or C ₃ -C ₃₀ polycyclic alicyclic ring or aromatic ring, the carbon atom of which can be replaced by at least one selected from nitrogen, oxygen and sulfur Hetero atom; G ring means substituted or unsubstituted C ₁ -C ₃₀ cycloalkyl, substituted or unsubstituted C ₆ -C ₃₀ aryl, or substituted or unsubstituted 3-30 member Heteroaryl; G ring may or may not exist; when G ring is absent, X, Y, Z represent -O-, -S-, -SO _2- , -C (R ₅ ) (R ₆ )-, -N (R ₇ )-, -Si (R ₅ ) (R ₆ )-, -Sn (R ₇ )-or -Ge (R ₇ )-; when G ring exists, X represents -SO _2- , -N (R ₇ )-, -Si (R ₅ ) (R ₆ )-, Sn (R ₇ )-or -Ge (R ₇ )-; Y, Z represent C, N, O, S atoms; R ₁ to R ₄ Each independently represents hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, substituted or unsubstituted C ₁ -C ₃₀ hydrocarbons, substituted or unsubstituted C ₁ -C ₃₀ alkoxy , Substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl, substituted or unsubstituted C ₃ -C ₃₀ cycloalkenyl, substituted or unsubstituted 3-7 membered heterocycloalkyl, substituted or unsubstituted C ₆ -C ₃₀ aromatic Group, substituted or unsubstituted 3-30 membered heteroaryl, -NR ₈ R ₉ , -SiR ₁₀ R ₁₁ R ₁₂ , -SR ₁₃ , -OR ₁₄ , -COR ₁₅ or -B (OR ₁₆ ) ( OR ₁₇ ); or connected with adjacent substituents to form a substituted or unsubstituted monocyclic or C ₃ -C ₃₀ polycyclic aliphatic ring or aromatic ring, the carbon atoms of which can be replaced by at least one selected from nitrogen and oxygen And sulfur heteroatoms; R ₅ to R ₁₇ each independently represent hydrogen, substituted or unsubstituted C ₁ -C ₃₀ alkyl, substituted or unsubstituted C ₆ -C ₃₀ aryl, or substituted Or an unsubstituted 3 to 30 membered heteroaryl; or connected to an adjacent substituent to form a substituted or unsubstituted monocyclic or C ₃ -C ₃₀ polycyclic aliphatic ring or aromatic ring; a, b and d independently represents integers 1 to 4; c represents integers 1 to 3; Hal is halogen.

The present disclosure also provides an organic electroluminescence device containing the above organic light-emitting compound.

The present disclosure also provides the use of the above-mentioned organic electroluminescent device in 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) .

detailed description

The technical problems in the present disclosure to be solved by the present disclosure include, for example, providing an organic light-emitting compound and a manufacturing method and an organic electroluminescent device of the compound. Power efficiency and long life.

The disclosure will be described in detail through specific embodiments. However, the following description is intended to explain the present disclosure, and is not intended to limit the scope of the present disclosure in any way.

The present disclosure provides an organic light emitting compound, the structural formula of which is as follows:

In the formula: Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, or a substituted or unsubstituted 3-30 membered heteroaryl; or connected with adjacent substituents to form a monocyclic or C ₃ -C ₃₀ polycyclic alicyclic ring or aromatic ring, the carbon atom of which can be replaced by at least one selected from nitrogen, oxygen and sulfur Of heteroatoms;

Ring G represents a substituted or unsubstituted C ₁ -C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, or a substituted or unsubstituted 3-30 membered heteroaryl group;

The G ring may or may not exist;

When G ring does not exist, X, Y, Z represent -O-, -S-, -SO _2- , -C (R ₅ ) (R ₆ )-, -N (R ₇ )-, -Si (R ₅ ) (R ₆ )-, -Sn (R ₇ )-or -Ge (R ₇ )-;

When the G ring exists, X represents -SO _2- , -N (R ₇ )-, -Si (R ₅ ) (R ₆ )-, Sn (R ₇ )-, or -Ge (R ₇ )-; Y, Z represent C, N, O, S atoms; R _{3 is} selected from hydrogen, or connected with adjacent substituents to form a substituted or unsubstituted monocyclic ring or C ₃ -C ₃₀ polycyclic aliphatic ring or aromatic ring, G ring Preferred are benzene ring, naphthalene ring, pyridine ring, 1-phenyl-1H-indole, benzofuran, benzothiophene, 4-phenyl-4H-benzo [b] [1,4] oxazine, 4- Phenyl-4H-benzothiazine, benzothiophene, 1,4-diphenyl-1,4-dihydroquinoxaline, 1,1,4,4-tetramethyl-1,4-dihydro Naphthalene

R ₁ to R ₄ each independently represent hydrogen, deuterium, halogen, cyano, carboxy, nitro, hydroxyl, substituted or unsubstituted C ₁ -C ₃₀ hydrocarbons, substituted or unsubstituted C _1- C ₃₀ alkoxy, substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl, substituted or unsubstituted C ₃ -C ₃₀ cycloalkenyl, substituted or unsubstituted 3-7 membered hetero Cycloalkyl, substituted or unsubstituted C ₆ -C ₃₀ aryl, substituted or unsubstituted 3-30 membered heteroaryl, -NR ₈ R ₉ , -SiR ₁₀ R ₁₁ R ₁₂ , -SR ₁₃ , -OR ₁₄ , -COR ₁₅ or -B (OR ₁₆ ) (OR ₁₇ ); or connected with adjacent substituents to form a substituted or unsubstituted monocyclic ring or C ₃ -C ₃₀ polycyclic aliphatic ring or Aromatic ring, its carbon atom can be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur

R ₅ to R ₁₇ each independently represent hydrogen, a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, or a substituted or unsubstituted 3 Up to 30-membered heteroaryl; or linked to adjacent substituents to form substituted or unsubstituted monocyclic or C ₃ -C ₃₀ polycyclic aliphatic or aromatic rings; in some embodiments, R ₇ is benzene , Cyano substituted benzene, or methyl;

a, b, and d each independently represent integers 1 to 4; c represents integers 1 to 3; in some embodiments, a, b, c, and d are all 1.

In some embodiments, Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted C ₁₀ -C ₂₅ aryl group, or a 13-25 membered heteroaryl group; further preferably Ar ₁ and Ar ₂ each independently represent Substituted or unsubstituted C ₁₄ -C ₂₁ aryl, or 17-23 membered heteroaryl; it is further preferred that Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted C ₁₆ -C ₁₉ aryl, Or 19-21 membered heteroaryl; further preferably Ar ₁ and Ar ₂ are benzene, 1,1 ′, 3 ′, 1 ″ -triphenyl, biphenyl, diaminobenzene, phenanthryl, naphthyl, 1- Phenylnaphthalene or 9,9-dimethylfluorene.

In some embodiments, the organic light-emitting compound is selected from any one of the following structures:

The present disclosure also provides a method for preparing an organic light-emitting compound, including the following steps:

Step 1. After adding Compound 2 and tetrahydrofuran to the reaction vessel, the vessel was cooled to -78 ° C under a nitrogen atmosphere, then n-butyllithium was added dropwise to the mixture, and after stirring the mixture at -78 ° C, It was stirred at room temperature and cooled to -78 ° C; thereafter, Compound 1 dissolved in tetrahydrofuran was added dropwise to the mixture; after the addition, the reaction temperature was raised to room temperature, and the mixture was stirred; then the chlorination An aqueous ammonium solution was added to the reaction solution to complete the reaction, and the reaction solution was extracted with ethyl acetate, followed by drying the extracted organic layer with magnesium sulfate, and the solvent was removed using a rotary evaporator, and the remaining material was purified by column chromatography to obtain an intermediate Body 1-1;

Step 2. After adding Intermediate 1-1, Compound 3 and methylene chloride to the reaction vessel, fully replace the air with nitrogen three times, and add boron trifluoride ether dissolved in methylene chloride dropwise to the mixture; After stirring the mixture at room temperature, it was quenched with distilled water, and the mixture was extracted with dichloromethane; then the extracted organic layer was dried using sodium sulfate, and the solvent was removed using a rotary evaporator, and the remaining material was purified by column chromatography to obtain intermediate 2;

Step 3. Intermediate 2, Ar ₁ Br and Ar ₂ Br, Pd ₂ (dba) ₃ , P (t-Bu) ₃ , NaOt-Bu, toluene are reacted; after the reaction is completed, the organic matter is extracted with ether and water. The concentrated product after the layer was dried with magnesium sulfate was used to obtain the compound of formula 1 by silica gel column and recrystallization method;

The synthetic route is as follows:

In the formula: Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, or a substituted or unsubstituted 3-30 membered heteroaryl; or connected with adjacent substituents to form a monocyclic or C ₃ -C ₃₀ polycyclic alicyclic ring or aromatic ring, the carbon atom of which can be replaced by at least one selected from nitrogen, oxygen and sulfur Hetero atom; G ring means substituted or unsubstituted C ₁ -C ₃₀ cycloalkyl, substituted or unsubstituted C ₆ -C ₃₀ aryl, or substituted or unsubstituted 3-30 member Heteroaryl; G ring may or may not exist; when G ring is absent, X, Y, Z represent -O-, -S-, -SO _2- , -C (R ₅ ) (R ₆ )-, -N (R ₇ )-, -Si (R ₅ ) (R ₆ )-, -Sn (R ₇ )-or -Ge (R ₇ )-; when G ring exists, X represents -SO _2- , -N (R ₇ )-, -Si (R ₅ ) (R ₆ )-, Sn (R ₇ )-or -Ge (R ₇ )-; Y, Z represent C, N, O, S atoms; R ₁ to R ₄ Each independently represents hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, substituted or unsubstituted C ₁ -C ₃₀ hydrocarbons, substituted or unsubstituted C ₁ -C ₃₀ alkoxy , Substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl, substituted or unsubstituted C ₃ -C ₃₀ cycloalkenyl, substituted or unsubstituted 3-7 membered heterocycloalkyl, substituted or unsubstituted C ₆ -C ₃₀ aromatic Group, substituted or unsubstituted 3-30 membered heteroaryl, -NR ₈ R ₉ , -SiR ₁₀ R ₁₁ R ₁₂ , -SR ₁₃ , -OR ₁₄ , -COR ₁₅ or -B (OR ₁₆ ) ( OR ₁₇ ); or connected with adjacent substituents to form a substituted or unsubstituted monocyclic or C ₃ -C ₃₀ polycyclic aliphatic ring or aromatic ring, the carbon atoms of which can be replaced by at least one selected from nitrogen and oxygen And sulfur heteroatoms; R ₅ to R ₁₇ each independently represent hydrogen, substituted or unsubstituted C ₁ -C ₃₀ alkyl, substituted or unsubstituted C ₆ -C ₃₀ aryl, or substituted Or an unsubstituted 3 to 30 membered heteroaryl; or connected to an adjacent substituent to form a substituted or unsubstituted monocyclic or C ₃ -C ₃₀ polycyclic aliphatic ring or aromatic ring; a, b and d independently represents integers 1 to 4; c represents integers 1 to 3; Hal is halogen.

The organic electroluminescent compound according to the present disclosure may be included in at least one of the light emitting layer and the hole transport layer.

The present disclosure also provides an organic electroluminescence device containing the above organic light-emitting compound.

In some embodiments, the organic electroluminescent device includes: a first electrode, a second electrode, and an organic layer disposed between the two electrodes, wherein the organic layer includes at least one type 1 The compound of the structure shown; the compound of the structure shown in Formula 1 may be in a single form or mixed with other substances in the organic layer.

One of the first and second electrodes is an anode, and the other is a cathode. The organic layer includes a light-emitting layer, and preferably includes at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, a hole blocking layer, and an electron blocking layer.

In some embodiments, the organic layer includes at least a hole injection layer, a hole transport layer, a layer having both hole injection and hole transport skills, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer , One or more of the electron injection layer and the layer with both electron transmission and electron injection skills.

The term “organic layer” in the present disclosure refers to the term of all layers disposed between the first electrode and the second electrode of the organic electroluminescent device.

When the compound of formula 1 is present in the light-emitting layer of the organic layer, the compound of formula 1 can be used as a light-emitting host or doped in other fluorescent hosts;

When the compound of formula 1 is present in the hole transport layer or hole injection layer in the organic layer, the compound of formula 1 can be used as a hole transport layer, a hole injection layer, and both With hole transport common energy layer.

The device prepared by the compound containing the structure of formula 1 described in this disclosure can be used for organic light emitting device (OLED), organic solar cell (OSC), electronic paper (e-Paper), organic photoreceptor (OPC) or organic thin film transistor (OTFT).

The organic electroluminescent device described in the present disclosure can form an anode by vapor-depositing metal, conductive oxides and their alloys on a substrate by thin film evaporation, electron beam evaporation, physical vapor deposition, etc., or spin coating Film (spin-coating) or thin-band lead evaporation; tape-casting, doctor-blading, screen-printing, inkjet printing or thermal imaging (Thermal- Imaging) and other methods to reduce the number of layers manufacturing.

The present disclosure relates to an organic light-emitting compound of Formula 1 and a preparation method thereof, and an organic electroluminescent device containing the compound.

The beneficial effects of this disclosure are:

The present disclosure provides a hole transport material used in an organic EL device that can solve conventional technical problems. The traditional hole transport materials are mainly based on triaryl derivatives. Although it has a hole-transporting ability and a low driving voltage, in order to obtain a suitable glass transition temperature, it has to introduce a large number of substituents in its structure to increase its molecular weight. However, this reduces the triplet energy or LUMO energy, which leads to the deterioration of the organic electroluminescent device. The ideal hole transport material requires a high glass transition temperature, hole injection ability and hole transport ability, as well as suitable triplet energy and LUMO energy. Therefore, in order to solve the problems existing in the conventional hole transport materials and obtain an ideal material, the present disclosure proposes a solution of introducing an arylamine and a heterocyclic ring to the 9-position of fluorene. By introducing arylamines, hole injection / transport capabilities, high power efficiency, and long life are obtained; by introducing heterocycles, an appropriate glass transition temperature is obtained, thereby obtaining high-quality organic electroluminescent materials.

The organic electroluminescent device prepared from the organic light-emitting compound of the present disclosure has excellent current efficiency and power efficiency and long life.

The preparation method of the organic light-emitting compound of the present disclosure has good repeatability and high yield.

Example 1: Preparation of compound 1

After adding 4-bromo-9-phenylcarbazole (60 mmol) and 200 mL of tetrahydrofuran to the reaction vessel, the vessel was cooled to -78 ° C under a nitrogen atmosphere. Then n-butyllithium (2.5M, 60 mmol) was slowly added dropwise to the mixture. After the mixture was stirred at -78 ° C for 30 minutes, it was stirred at room temperature for 3 hours, and cooled to -78 ° C. Thereafter, fluorenone (60 mmol) dissolved in 200 mL of tetrahydrofuran was slowly added dropwise to the mixture. After the addition, the reaction temperature was slowly raised to room temperature, and the mixture was stirred for 16 hours. Next, an aqueous ammonium chloride solution was added to the reaction solution to complete the reaction, and the reaction solution was extracted with ethyl acetate. Next, the extracted organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography to obtain compound 1-1 (19.04 g, 75%, mass spectrum value: 423.42).

After compound 1-1 (45 mmol), 2,3,5,6-deuterated aniline (46 mmol) and 500 L of dichloromethane were added to the reaction vessel, the air was sufficiently replaced with nitrogen three times, and dissolved in 100 mL of dichloromethane Boron trifluoride etherate (46 mmol) was slowly added dropwise to the mixture. After stirring the mixture at room temperature for 2 hours, it was quenched with distilled water, and the mixture was extracted with dichloromethane. Next, the extracted organic layer was dried using sodium sulfate, and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography to obtain compound 3-1 (41.85 mmol, 93%, mass spectrum value: 502.25).

27.2mmol compound 3-1 and 27.2mmol bromobenzene, Pd ₂ (dba) ₃ (2.64g, 2.89mmol), P (t-Bu) ₃ (1.17g, 5.78mmol), NaOt-Bu (16.7g, 173.5 mmol), toluene 600mL reaction at 100 ℃. After the reaction was completed, the organic matter was extracted with ether and water. The organic layer was dried over magnesium sulfate. The concentrated product was subjected to silica gel column and recrystallization method to obtain 18.22 mmol of Compound 1 (67%) with a mass spectrum value of 654.32.

Example 2: Preparation of compound 7

According to the above synthetic route, compound 7 was prepared according to the method of Example 1 (yield = 75% mass spectrometry value: 682.35).

Example 3: Preparation of compound 13

According to the above synthetic route, compound 13 was prepared according to the method of Example 1 (yield = 78% mass spectrum value: 780.36).

Example 4: Preparation of compound 17

According to the above synthetic route, compound 17 was prepared according to the method of Example 1 (yield = 83% mass spectrometry value: 846.41).

Example 5: Preparation of compound 18

Following the above synthetic route, compound 18 was prepared according to the method of Example 1 (yield = 79% mass spectrometry value: 862.40).

Example 6: Preparation of compound 20

According to the above synthetic route, compound 20 was prepared according to the method of Example 1 (yield = 85% mass spectrometry value: 888.46).

Example 7: Preparation of compound 28

Following the above synthetic route, compound 28 was prepared according to the method of Example 1 (yield = 86% mass spectrometry value: 819.34).

Example 8: Preparation of compound 31

According to the above synthetic route, compound 31 was prepared according to the method of Example 1 (yield = 77% mass spectrometry value: 984.43).

Example 9: Preparation of compound 35

According to the above synthetic route, compound 35 was prepared according to the method of Example 1 (yield = 81% mass spectrometry value: 925.34).

Example 10: Preparation of compound 40

According to the above synthetic route, compound 40 was prepared according to the method of Example 1 (yield = 82% mass spectrometry value: 986.44).

Example 11: Preparation of compound 41

According to the above synthetic route, compound 41 was prepared according to the method of Example 1 (yield = 87% mass spectrometry value: 655.32).

Example 12: Preparation of compound 42

According to the above synthetic route, compound 42 was prepared according to the method of Example 1 (yield = 79% mass spectrum value: 858.40).

Example 13: Preparation of compound 45

According to the above synthetic route, compound 45 was prepared according to the method of Example 1 (yield = 86% mass spectrometry value: 910.42).

Example 14: Preparation of compound 46

According to the above synthetic route, compound 46 was prepared according to the method of Example 1 (yield = 85% mass spectrometry value: 704.32).

Example 15: Preparation of compound 51

According to the above synthetic route, compound 51 was prepared according to the method of Example 1 (yield = 88% mass spectrum value: 895.40).

Example 16: Preparation of compound 54

According to the above synthetic route, compound 54 was prepared according to the method of Example 1 (yield = 83% mass spectrometry value: 740.57).

Example 17: Preparation of compound 61

According to the above synthetic route, compound 61 was prepared according to the method of Example 1 (yield = 84% mass spectrometry value: 804.06).

Example 18: Preparation of compound 77

According to the above synthetic route, compound 77 was prepared according to the method of Example 1 (yield = 85% mass spectrometry value: 829.64).

Example 19: Manufacturing an organic electroluminescent device containing Compound 1

的ITO玻璃基板放在蒸馏水中清洗2次，超声波洗涤30分钟，用蒸馏水反复清洗2次，超声波洗涤10分钟，蒸馏水清洗结束后，异丙醇、丙酮、甲醇等溶剂按顺序超声波洗涤以后干燥，转移到等离子体清洗机里，将上述基板洗涤5分钟，送到蒸镀机里。将已经准备好的ITO透明电极上蒸镀厚度为50nm的4,4',4”-三[2-萘基苯基氨基]三苯基胺(2-TNATA)作为空穴注入层。然后将化合物1在形成的空穴注入层上面真空蒸镀厚度为30nm的空穴传输层。然后在上述空穴传输层上蒸镀厚度为30nm的蓝色主体材料9,10-二(2-萘基)蒽(ADN)和掺杂材料双(4,6-二氟苯基吡啶-N,C ²)吡啶甲酰合铱(FIrpic)。主体材料和掺杂材料的重量比为95:5。接着在上述发光层上真空蒸镀厚度为40nm的TPBi作为空穴阻挡层及电子传输层。在上述电子传输层上真空蒸镀厚度为0.5nm氟化锂(LiF)，作为电子注入层。最后蒸镀厚度为150nm的铝作为阴极，以此完成了有机电致发光器件的制备。对得到的器件的性能发光特性测试，测量采用KEITHLEY 2400型源测量单元，CS-2000分光辐射亮度计，以评价驱动电压，发光亮度，发光效率。 The coating thickness is

The ITO glass substrate was washed twice in distilled water, ultrasonically washed for 30 minutes, repeatedly washed with distilled water twice, and ultrasonically washed for 10 minutes. After the distilled water was cleaned, isopropyl alcohol, acetone, methanol and other solvents were ultrasonically washed in sequence and dried. Transfer to a plasma cleaner, wash the substrate for 5 minutes, and send it to a vapor deposition machine. 4,4 ', 4 "-tri [2-naphthylphenylamino] triphenylamine (2-TNATA) with a thickness of 50nm was deposited on the prepared ITO transparent electrode as a hole injection layer. Then, Compound 1 vacuum-deposits a hole transport layer with a thickness of 30 nm on the formed hole injection layer. Then, a blue host material 9,10-bis (2-naphthyl) with a thickness of 30 nm is vapor-deposited on the hole transport layer ) Anthracene (ADN) and doped material bis (4,6-difluorophenylpyridine-N, C ² ) pyridineformyl iridium (FIrpic). The weight ratio of host material and doped material is 95: 5. TPBi with a thickness of 40 nm is vacuum-evaporated on the light-emitting layer as a hole blocking layer and an electron transport layer. Lithium fluoride (LiF) with a thickness of 0.5 nm is vacuum-evaporated on the electron-transport layer as an electron injection layer. Aluminium plated with a thickness of 150nm was used as the cathode to complete the preparation of the organic electroluminescent device. For the performance of the obtained device, the luminescence characteristics were tested by using a KEITHLEY 2400 source measurement unit and a CS-2000 spectroradiometer to evaluate Driving voltage, luminous brightness, luminous efficiency.

Example 20: Fabrication of an organic electroluminescent device containing compound 7

The compound 1 in Example 19 was replaced with the compound 7, and the organic electroluminescent device containing the compound 7 was produced in the same manner as the other methods.

Example 21: Fabrication of an organic electroluminescent device containing compound 13

The compound 1 in Example 19 was replaced with the compound 13, and the organic EL device containing the compound 13 was produced in the same manner as in the other methods.

Example 22: Fabrication of an organic electroluminescent device containing compound 17

The compound 1 in Example 19 was replaced with the compound 17, and the organic electroluminescent device containing the compound 17 was produced in the same manner as the other methods.

Example 23: Fabrication of an organic electroluminescent device containing compound 18

The compound 1 in Example 19 was replaced with the compound 18, and other methods were the same. An organic electroluminescent device containing the compound 18 was produced.

Example 24: Manufacture of an organic electroluminescent device containing compound 20

The compound 1 in Example 19 was replaced with the compound 20, and the organic EL device containing the compound 20 was produced in the same manner as the other methods.

Example 25: Fabrication of an organic electroluminescent device containing compound 28

The compound 1 in Example 19 was replaced with the compound 28, and the organic EL device containing the compound 28 was produced in the same manner as in the other methods.

Example 26: Fabrication of an organic electroluminescent device containing compound 31

The compound 1 in Example 19 was replaced with the compound 31, and the organic EL device containing the compound 31 was produced in the same manner as the other methods.

Example 27: Fabrication of an organic electroluminescent device containing compound 35

The compound 1 in Example 19 was replaced with the compound 35, and other methods were the same, and an organic electroluminescence device containing the compound 35 was produced.

Example 28: Manufacture of an organic electroluminescent device containing compound 40

The compound 1 in Example 19 was replaced with the compound 40, and the organic EL device containing the compound 40 was produced in the same manner as in the other methods.

Example 29: Manufacture of an organic electroluminescent device containing compound 41

The compound 1 in Example 19 was replaced with the compound 41, and the organic EL device containing the compound 41 was produced in the same manner as in the other methods.

Example 30: Fabrication of an organic electroluminescent device containing compound 42

The compound 1 in Example 19 was replaced with the compound 42, and other methods were the same, and an organic electroluminescence device containing the compound 42 was produced.

Example 31: Fabrication of an organic electroluminescent device containing compound 45

The compound 1 in Example 19 was replaced with the compound 45, and other methods were the same, and an organic electroluminescence device containing the compound 45 was produced.

Example 32: Manufacture of an organic electroluminescent device containing compound 46

The compound 1 in Example 19 was replaced with the compound 46, and other methods were the same, and an organic electroluminescence device containing the compound 46 was produced.

Example 33: Fabrication of an organic electroluminescent device containing compound 51

The compound 1 in Example 19 was replaced with the compound 51, and other methods were the same, and an organic electroluminescence device containing the compound 51 was produced.

Example 34: Fabrication of an organic electroluminescent device containing compound 54

The compound 1 in Example 19 was replaced with the compound 54, and other methods were the same, and an organic electroluminescence device containing the compound 54 was produced.

Example 35: Fabrication of an organic electroluminescent device containing compound 61

The compound 1 in Example 19 was replaced with the compound 61, and other methods were the same, and an organic electroluminescence device containing the compound 61 was produced.

Example 36: Manufacture of an organic electroluminescent device containing compound 77

The compound 1 in Example 19 was replaced with the compound 77, and other methods were the same, and an organic electroluminescence device containing the compound 77 was produced.

Comparative example 1:

According to the method of Example 19, the material of the hole transport layer was replaced by Compound 1 with N'-bis (1-naphthyl) -N, N'-diphenyl- (1,1'-biphenyl) -4 , 4'-diamine (NPD).

Table 1 shows the test results of the luminescence characteristics of the compounds prepared by the examples of the present disclosure and the organic electroluminescent devices prepared by a-NPD.

Table 1

From the above table, it can be seen that the compounds provided by the cost disclosure have suitable glass transition temperatures, and the luminous efficiency and life span of the organic electroluminescent devices prepared from them are significantly improved compared to the organic electroluminescent devices prepared from a-NPD.

The descriptions of the above embodiments are only used to help understand the method and the core idea of the present disclosure. It should be noted that, for those of ordinary skill in the art, without departing from the principles of the present disclosure, several improvements and modifications can be made to the present disclosure, and these improvements and modifications also fall within the protection scope of the claims of the present disclosure.

Industrial applicability

The present disclosure provides an organic light-emitting compound, hole injection capability / transport capability, high power efficiency, and long life are obtained by introducing an arylamine; an appropriate glass transition temperature is obtained by introducing a heterocyclic ring, thereby obtaining high-quality organic electricity Luminescent material. The preparation method of the organic luminescent compound provided by the present disclosure has good repeatability and high yield. The organic electroluminescent device prepared from the organic light emitting compound of the present disclosure has excellent current efficiency and power efficiency and long life.

Claims (15)

An organic luminescent compound, characterized in that its structural formula is as follows:

In the formula: Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, or a substituted or unsubstituted 3-30 membered heteroaryl; or connected with adjacent substituents to form a monocyclic or C ₃ -C ₃₀ polycyclic alicyclic ring or aromatic ring, the carbon atom of which can be replaced by at least one selected from nitrogen, oxygen and sulfur Of heteroatoms; Ring G represents a substituted or unsubstituted C ₁ -C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, or a substituted or unsubstituted 3-30 membered heteroaryl group; The G ring may or may not exist; When G ring does not exist, X, Y, Z represent -O-, -S-, -SO _2- , -C (R ₅ ) (R ₆ )-, -N (R ₇ )-, -Si (R ₅ ) (R ₆ )-, -Sn (R ₇ )-or -Ge (R ₇ )-; When the G ring exists, X represents -SO _2- , -N (R ₇ )-, -Si (R ₅ ) (R ₆ )-, Sn (R ₇ )-, or -Ge (R ₇ )-; Y, Z represent C, N, O, S atoms; R ₁ to R ₄ each independently represent hydrogen, deuterium, halogen, cyano, carboxy, nitro, hydroxyl, substituted or unsubstituted C ₁ -C ₃₀ hydrocarbons, substituted or unsubstituted C _1- C ₃₀ alkoxy, substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl, substituted or unsubstituted C ₃ -C ₃₀ cycloalkenyl, substituted or unsubstituted 3-7 membered hetero Cycloalkyl, substituted or unsubstituted C ₆ -C ₃₀ aryl, substituted or unsubstituted 3-30 membered heteroaryl, -NR ₈ R ₉ , -SiR ₁₀ R ₁₁ R ₁₂ , -SR ₁₃ , -OR ₁₄ , -COR ₁₅ or -B (OR ₁₆ ) (OR ₁₇ ); or connected with adjacent substituents to form a substituted or unsubstituted monocyclic ring or C ₃ -C ₃₀ polycyclic aliphatic ring or Aromatic ring, its carbon atom can be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur R ₅ to R ₁₇ each independently represent hydrogen, a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, or a substituted or unsubstituted 3 Up to 30-membered heteroaryl; or linked to adjacent substituents to form substituted or unsubstituted monocyclic or C ₃ -C ₃₀ polycyclic aliphatic or aromatic rings; a, b, and d independently represent integers 1 to 4; c represents integers 1 to 3. The organic light-emitting compound according to claim 1, wherein Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted C ₁₀ -C ₂₅ aryl group or a 13-25 membered heteroaryl group. The organic light-emitting compound according to claim 1 or 2, wherein Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted C ₁₄ -C ₂₁ aryl group or a 17-23 membered heteroaryl group. The organic light-emitting compound according to any one of claims 1 to 3, wherein Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted C ₁₆ -C ₁₉ aryl group, or 19-21 member Heteroaryl. The organic light-emitting compound according to any one of claims 1 to 4, wherein Ar ₁ and Ar ₂ are each independently represented as benzene, 1,1 ′, 3 ′, 1 ″ -triphenyl, biphenyl Group, diaminobenzene, phenanthrenyl, naphthyl, 1-phenylnaphthalene or 9,9-dimethylfluorene. The organic light-emitting compound according to any one of claims 1 to 7, wherein a, b, c, and d are all 1. The organic light-emitting compound according to any one of claims 1-7, wherein the G ring is a benzene ring, a naphthalene ring, a pyridine ring, 1-phenyl-1H-indole, benzofuran, benzothiophene , 4-phenyl-4H-benzo [b] [1,4] oxazine, 4-phenyl-4H-benzothiazine, benzothiophene, 1,4-diphenyl-1,4-di Hydroquinoxaline, or 1,1,4,4-tetramethyl-1,4-dihydronaphthalene. The organic light-emitting compound according to any one of claims 1-7, characterized in that it is selected from any one of the following structures:

A method for preparing an organic light-emitting compound according to claim 1, comprising the following steps: Step 1. After adding Compound 2 and tetrahydrofuran to the reaction vessel, the vessel was cooled to -78 ° C under a nitrogen atmosphere, then n-butyllithium was added dropwise to the mixture, and after stirring the mixture at -78 ° C, It was stirred at room temperature and cooled to -78 ° C; thereafter, Compound 1 dissolved in tetrahydrofuran was added dropwise to the mixture; after the addition, the reaction temperature was raised to room temperature, and the mixture was stirred; then the chlorination An aqueous ammonium solution was added to the reaction solution to complete the reaction, and the reaction solution was extracted with ethyl acetate, followed by drying the extracted organic layer with magnesium sulfate, and the solvent was removed using a rotary evaporator, and the remaining material was purified by column chromatography to obtain an intermediate Body 1-1; Step 2. After adding Intermediate 1-1, Compound 3 and methylene chloride to the reaction vessel, fully replace the air with nitrogen three times, and add boron trifluoride ether dissolved in methylene chloride dropwise to the mixture; After stirring the mixture at room temperature, it was quenched with distilled water, and the mixture was extracted with dichloromethane; then the extracted organic layer was dried using sodium sulfate, and the solvent was removed using a rotary evaporator, and the remaining material was purified by column chromatography to obtain intermediate 2; Step 3. Intermediate 2, Ar ₁ Br and Ar ₂ Br, Pd ₂ (dba) ₃ , P (t-Bu) ₃ , NaOt-Bu, toluene are reacted; after the reaction is completed, the organic matter is extracted with ether and water. The concentrated product after the layer was dried with magnesium sulfate was used to obtain the compound of formula 1 by silica gel column and recrystallization method; The synthetic route is as follows:

In the formula: Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, or a substituted or unsubstituted 3-30 membered heteroaryl; or connected with adjacent substituents to form a monocyclic or C ₃ -C ₃₀ polycyclic alicyclic ring or aromatic ring, the carbon atom of which can be replaced by at least one selected from nitrogen, oxygen and sulfur Hetero atom; G ring means substituted or unsubstituted C ₁ -C ₃₀ cycloalkyl, substituted or unsubstituted C ₆ -C ₃₀ aryl, or substituted or unsubstituted 3-30 member Heteroaryl; G ring may or may not exist; when G ring is absent, X, Y, Z represent -O-, -S-, -SO _2- , -C (R ₅ ) (R ₆ )-, -N (R ₇ )-, -Si (R ₅ ) (R ₆ )-, -Sn (R ₇ )-or -Ge (R ₇ )-; when G ring exists, X represents -SO _2- , -N (R ₇ )-, -Si (R ₅ ) (R ₆ )-, Sn (R ₇ )-or -Ge (R ₇ )-; Y, Z represent C, N, O, S atoms; R ₁ to R ₄ Each independently represents hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, substituted or unsubstituted C ₁ -C ₃₀ hydrocarbons, substituted or unsubstituted C ₁ -C ₃₀ alkoxy , Substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl, substituted or unsubstituted C ₃ -C ₃₀ cycloalkenyl, substituted or unsubstituted 3-7 membered heterocycloalkyl, substituted or unsubstituted C ₆ -C ₃₀ aromatic Group, substituted or unsubstituted 3-30 membered heteroaryl, -NR ₈ R ₉ , -SiR ₁₀ R ₁₁ R ₁₂ , -SR ₁₃ , -OR ₁₄ , -COR ₁₅ or -B (OR ₁₆ ) ( OR ₁₇ ); or connected with adjacent substituents to form a substituted or unsubstituted monocyclic or C ₃ -C ₃₀ polycyclic aliphatic ring or aromatic ring, the carbon atoms of which can be replaced by at least one selected from nitrogen and oxygen And sulfur heteroatoms; R ₅ to R ₁₇ each independently represent hydrogen, substituted or unsubstituted C ₁ -C ₃₀ alkyl, substituted or unsubstituted C ₆ -C ₃₀ aryl, or substituted Or an unsubstituted 3 to 30 membered heteroaryl; or connected to an adjacent substituent to form a substituted or unsubstituted monocyclic or C ₃ -C ₃₀ polycyclic aliphatic ring or aromatic ring; d independently represents integers 1 to 4; c represents integers 1 to 3; Hal is halogen. An organic electroluminescent device containing the organic light-emitting compound according to any one of claims 1-8. The organic electroluminescent device according to claim 10, comprising a first electrode, a second electrode, and an organic layer interposed between the first and second electrodes. The organic electroluminescent device according to claim 11, wherein the organic layer comprises a compound of formula 1. The organic electroluminescent device according to claim 12, wherein the compound containing the structure of Formula 1 may exist in the organic layer in a single form or mixed with other substances. The organic electroluminescent device according to claim 11, wherein the organic layer includes at least a hole injection layer, a hole transport layer, a layer having both hole injection and hole transport skills, and an electron blocking layer , One or more of the group consisting of light emitting layer, hole blocking layer, electron transport layer, electron injection layer and both electron transport and electron injection skill layer. The organic electroluminescent device according to claim 10 in 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) use.