CN109748898B - Organic electroluminescent compound, preparation method thereof and organic electroluminescent device - Google Patents

Organic electroluminescent compound, preparation method thereof and organic electroluminescent device Download PDF

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CN109748898B
CN109748898B CN201811640915.3A CN201811640915A CN109748898B CN 109748898 B CN109748898 B CN 109748898B CN 201811640915 A CN201811640915 A CN 201811640915A CN 109748898 B CN109748898 B CN 109748898B
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organic electroluminescent
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王辉
李文军
黄悦
陈明
李建行
姜晓晨
马晓宇
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The invention relates to the technical field of luminescent materials, in particular to an organic electroluminescent compound, a preparation method thereof and an organic electroluminescent device. In order to solve the problems existing in the conventional hole transport materials and obtain ideal materials, the present invention proposes a solution for introducing aryl amine and heterocycle to the 9-position of xanthene. Hole injection capacity/transport capacity, high power efficiency and long service life are obtained by introducing arylamine; by introducing a heterocycle, a proper glass transition temperature is obtained, so that a high-quality organic electroluminescent material is obtained. Devices made from the compounds provided herein have excellent current and power efficiency and long life. The preparation method of the organic electroluminescent compound provided by the invention is simple and feasible, has high yield and is suitable for industrial production.

Description

Organic electroluminescent compound, preparation method thereof and organic electroluminescent device
Technical Field
The invention relates to the technical field of luminescent materials, in particular to an organic electroluminescent compound, a preparation method thereof and an organic electroluminescent device.
Background
Electroluminescent devices (EL devices) are automatic light emitting devices that have the advantage of providing a wide viewing angle, a large contrast ratio, and a fast response time.
The organic EL element is a self-luminous element utilizing the following principle: by applying an electric field, the fluorescent substance emits light by the recombination energy of holes injected from the anode and electrons injected from the cathode. It has a structure of an anode, a cathode, and an organic layer interposed therebetween. In order to improve efficiency and stability of the organic EL element, the organic material layer includes a plurality of layers having different materials, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), a light emitting layer, an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL).
In such an organic EL device, 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 having a specific wavelength when they migrate to the ground state.
The most important factor determining the luminous efficiency in an organic EL device is a light emitting material. Up to now, fluorescent materials have been widely used as luminescent materials. However, in view of the electroluminescent mechanism, development of phosphorescent light emitting materials has been widely studied because phosphorescent materials theoretically enhance the light emitting efficiency four times as compared with fluorescent materials. Iridium (III) complexes have been widely referred to as phosphorescent dopant materials. Currently, 4'-N, N' -dicarbazole-biphenyl (CBP), 9, 10-bis (2-naphthyl) Anthracene (ADN), and the like are widely used as known phosphorescent host materials. While these materials provide good luminescence characteristics, they have the following drawbacks: (1) The lifetime of the device is reduced due to its lower glass transition temperature and poor thermal stability. (2) Organic EL devices comprising phosphorescent host materials require higher driving voltages. Meanwhile, in order to improve efficiency and stability of the organic EL device, it is required to have a multi-layered 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 may change hole transport efficiency, light emitting efficiency, lifetime, etc. of holes to the light emitting layer. Therefore, copper phthalocyanine (CuPc), 4' -bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl (NPB), N ' -diphenyl-N, N ' -bis (3-methylphenyl) - (1, 1' -biphenyl) -4,4' -diamine (TPD), or the like is used as the hole transport material. However, organic EL devices using these materials have problems in terms of quantum efficiency and lifetime, which need to be further improved.
Disclosure of Invention
The invention provides an organic electroluminescent compound, a preparation method thereof and an organic electroluminescent device, and the device prepared by the compound has excellent current efficiency, power efficiency and long service life.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides an organic electroluminescent compound, which has the following structural formula:
Figure BDA0001931112370000021
wherein:
Ar 1 and Ar is a group 2 Each independently represents a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, or an arylamine group;
or with adjacent substituents to form a single or multiple ring, in particular a C3-C30 cycloaliphatic or aromatic ring, the carbon atoms of which may be replaced by at least one heteroatom selected from nitrogen, oxygen and sulfur;
Ar 3 represents a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, an arylamine group or a fatty amine group;
or with adjacent substituents to form a single or multiple ring, in particular a C3-C30 cycloaliphatic or aromatic ring, the carbon atoms of which may be replaced by at least one heteroatom selected from nitrogen, oxygen and sulfur;
preferably said Ar 1 And Ar is a group 2 Each independently selected from substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C15-C26 heteroaryl or triarylamine groups, ar 3 Represents a substituted or unsubstituted C6-C25 aryl, a substituted or unsubstituted C5-C24 heteroaryl or a triarylamine group; further preferably said Ar 1 And Ar is a group 2 Each independently selected from warpA substituted or unsubstituted C10-C14 aryl, a substituted or unsubstituted C18-C22 heteroaryl, or a triphenylamine group; ar (Ar) 3 Represents a substituted or unsubstituted C10-C20 aryl, a substituted or unsubstituted C12-C18 heteroaryl or a triphenylamine group;
l is a substituted or unsubstituted C6-C30 aryl group; benzene or deuterated benzene is preferred;
x represents-O-, -S-, -SO 2 -Si-, -Sn-, or-Ge-;
R 1 and R is 2 Each independently represents hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, substituted or unsubstituted C1-C30 hydrocarbyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C3-C7 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, -NR 3 R 4 、-SiR 5 R 6 R 7 -、-SR 8 、-OR 9 、-COR 10 、-B(OR 11 )(OR 12 ) The method comprises the steps of carrying out a first treatment on the surface of the Preferably R 1 And R is 2 Hydrogen, methyl or isopropyl;
or R is 1 And R is 2 Is linked to adjacent substituents to form a substituted or unsubstituted mono-or polycyclic, in particular a C3-C30 cycloaliphatic or aromatic ring, the carbon atoms of which may be replaced by at least one heteroatom selected from nitrogen, oxygen and sulfur; preferably naphthalene, anthracene or pyrene, or substituted naphthalene, anthracene or pyrene; wherein the substituent is methyl or phenyl;
R 3 to R 12 Each independently represents a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group;
or with adjacent substituents to form a substituted or unsubstituted monocyclic or polycyclic, in particular a C3-C30 aliphatic or aromatic ring;
a, b are each integers from 1 to 4; preferably, a and b are 1.
In the above technical scheme, the organic electroluminescent compound is selected from compounds with structures shown in chemical formulas 2-4:
Figure BDA0001931112370000041
in the above technical scheme, the Ar 1 And Ar is a group 2 Each independently selected from the following structures:
Figure BDA0001931112370000051
the Ar is as follows 3 Selected from the following structures:
Figure BDA0001931112370000061
wherein R is hydrogen, halogen, cyano, C1-C30 alkyl, C6-C50 aryl, C7-C50 aralkyl, C7-C50 arylalkoxy, C7-C50 arylalkylmercapto or C5-C50 heteroaryl;
preferably R is hydrogen, benzene, methyl or isopropyl;
wherein the alkyl is a straight chain alkyl, branched alkyl, cycloalkyl, a straight chain alkyl substituted with at least 1 substituent, a branched alkyl substituted with at least 1 substituent, or a cycloalkyl substituted with at least 1 substituent; wherein the substituent groups are independently selected from one or more of halogen, cyano, hydroxyl and mercapto.
The aryl group is preferably an unsubstituted aryl group or an aryl group substituted with at least 1 substituent; wherein the substituents are independently selected from halogen, amino, cyano, nitro, hydroxy or mercapto;
the arylalkyl is preferably unsubstituted arylalkyl or arylalkyl substituted with at least 1 substituent; wherein the substituents are independently selected from halogen, amino, cyano, nitro, hydroxy or mercapto;
the arylalkoxy group is preferably an unsubstituted arylalkoxy group or an arylalkoxy group substituted with at least 1 substituent; wherein the substituents are independently selected from halogen, amino, cyano, nitro, hydroxy or mercapto;
the arylalkylmercapto group is preferably an unsubstituted arylalkylmercapto group or an arylalkylmercapto group substituted with at least 1 substituent; wherein the substituents are independently selected from halogen, amino, cyano, nitro, hydroxy or mercapto;
the heteroaryl is preferably unsubstituted heteroaryl or heteroaryl substituted with at least 1 substituent; wherein the heteroatom in the heteroaryl group is nitrogen, sulfur or oxygen; the substituent groups independently select halogen, amino, cyano, nitro, hydroxyl or sulfhydryl;
and the R represents any position of benzene ring where the R is located.
In the above technical scheme, the organic electroluminescent compound is selected from compounds with structures shown in chemical formulas 1-135:
Figure BDA0001931112370000081
Figure BDA0001931112370000091
Figure BDA0001931112370000101
Figure BDA0001931112370000111
the invention also provides a preparation method of the organic electroluminescent compound, which comprises the following steps:
step 1, preparation of intermediate 1
Dissolving a compound 2 in tetrahydrofuran, adding n-butyllithium, uniformly stirring, adding the compound 1 dissolved in tetrahydrofuran, and stirring at room temperature for reaction to prepare an intermediate 1;
step 2, preparation of the Compound of chemical formula 1
Dissolving the intermediate 1 and the compound 3 in dichloromethane, then adding boron trifluoride diethyl etherate dissolved in the dichloromethane, and stirring at room temperature for reaction to prepare a compound shown in a chemical formula 1;
the synthetic route is as follows:
Figure BDA0001931112370000112
wherein R is 1 And R is 2 、X、Ar 1 、Ar 2 、Ar 3 L, and a and b are as defined in the above chemical formula 1, and Hal represents halogen.
In the above technical solution, the step 1 specifically includes the following steps:
after adding compound 2 and tetrahydrofuran to a reaction vessel, the vessel was cooled to-78 ℃ under nitrogen atmosphere; n-butyllithium was then slowly added dropwise to the foregoing mixture, after stirring the mixture at-78 ℃ for 30 minutes, it was stirred at room temperature for 3 hours, and cooled to-78 ℃; thereafter, compound 1 dissolved in tetrahydrofuran was slowly added dropwise to the mixture; after the addition, the reaction temperature was slowly warmed to room temperature, and the mixture was stirred for 16 hours; then adding an aqueous ammonium chloride solution to the reaction solution to complete the reaction, and extracting the reaction solution with ethyl acetate; the extracted organic layer was then dried using magnesium sulfate and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography to afford intermediate 1.
In the above technical solution, the step 2 specifically includes the following steps:
after intermediate 1, compound 3 and methylene chloride were added to the reaction vessel, air was sufficiently replaced with nitrogen three times; boron trifluoride diethyl etherate dissolved in 100mL of dichloromethane was slowly added dropwise to the foregoing mixture; after stirring the mixture at room temperature for 2 hours, it was quenched with distilled water and the mixture was extracted with dichloromethane; the extracted organic layer was then dried over sodium sulfate and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography to obtain a compound represented by chemical formula 1.
The invention also provides an organic electroluminescent device containing the organic electroluminescent compound.
In the above technical solution, the organic electroluminescent device includes:
the electrode comprises a first electrode, a second electrode and an organic matter layer arranged between the two electrodes, wherein the organic matter layer comprises at least one compound with a structure shown in a chemical formula 1; the compound of the structure shown in chemical formula 1 may exist in the organic layer in a single form or mixed with other substances. The above-mentioned materials may contain the organic electroluminescent compound according to the present invention alone, or may further include conventional materials generally used for organic electroluminescent materials. 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 further includes at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron injection layer, a hole blocking layer, and an electron blocking layer.
The organic electroluminescent compound according to the present invention may be contained in at least one of the light emitting layer and the hole transporting layer.
The organic layer at least comprises one or more of a hole injection layer, a hole transport layer, a layer with hole injection and hole transport skills, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a layer with electron transport and electron injection skills.
In the present invention, the term "organic layer" refers to the entire layer disposed between the first electrode and the second electrode of the organic electroluminescent device.
When the compound of the structure shown in chemical formula 1 exists in the light emitting layer in the organic layer, the compound of the structure shown in chemical formula 1 may be used as a light emitting host or doped in other fluorescent hosts;
when the compound of the structure shown in chemical formula 1 exists in the hole transport layer or the hole injection layer in the organic layer, the compound of the structure shown in chemical formula 1 may be used as a hole transport layer, a hole injection layer, and a layer having both hole injection and hole transport functions.
The device prepared by the compound with the structure shown in the chemical formula 1 can be used for an Organic Light Emitting Device (OLED), an Organic Solar Cell (OSC), electronic Paper (e-Paper), an Organic Photoconductor (OPC) or an Organic Thin Film Transistor (OTFT).
The device can be used for evaporating metal, conductive oxide and alloy thereof on a substrate to form an anode by methods such as film evaporation, electron beam evaporation, physical vapor deposition and the like, and spin-coating or thin-strip head evaporation can also be used; the number of layers can be reduced by molding (tape-casting), doctor blade (doctor-blading), screen Printing (Screen-Printing), ink jet Printing or Thermal Imaging (Thermal-Imaging).
The beneficial effects of the invention are as follows:
the present invention provides a hole transport material that can be used in an organic EL device and that can solve the conventional technical problems. Conventional hole transport materials are essentially based on triaryl derivatives. Although it has hole transporting ability and low driving voltage, a large number of substituents have to be introduced into its structure to raise its molecular weight in order to obtain a suitable glass transition temperature. But this reduces triplet energy or LUMO energy, resulting in degradation of the organic electroluminescent device. Ideal hole transporting materials require high glass transition temperatures, hole injection and hole transport capabilities, as well as suitable triplet energy and LUMO energy. Accordingly, in order to solve the problems existing in the conventional hole transport materials and to obtain an ideal material, the present invention proposes a solution for introducing arylamine and heterocycle to the 9-position of xanthene. Hole injection capacity/transport capacity, high power efficiency and long service life are obtained by introducing arylamine; by introducing a heterocycle, a proper glass transition temperature is obtained, so that a high-quality organic electroluminescent material is obtained.
Devices made from the compounds provided herein have excellent current and power efficiency and long life.
The preparation method of the organic electroluminescent compound provided by the invention is simple and feasible, has high yield and is suitable for industrial production.
Detailed Description
The invention provides an organic electroluminescent compound, which has the following structural formula:
Figure BDA0001931112370000141
wherein: ar (Ar) 1 And Ar is a group 2 Each independently represents a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, or an arylamine group; or with adjacent substituents to form a single or multiple ring, in particular a C3-C30 cycloaliphatic or aromatic ring, the carbon atoms of which may be replaced by at least one heteroatom selected from nitrogen, oxygen and sulfur; ar (Ar) 3 Represents a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, an arylamine group or a fatty amine group; or with adjacent substituents to form a single or multiple ring, in particular a C3-C30 cycloaliphatic or aromatic ring, the carbon atoms of which may be replaced by at least one heteroatom selected from nitrogen, oxygen and sulfur; preferably said Ar 1 And Ar is a group 2 Each independently selected from substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C15-C26 heteroaryl or triarylamine groups, ar 3 Represents a substituted or unsubstituted C6-C25 aryl, a substituted or unsubstituted C5-C24 heteroaryl or a triarylamine group; further preferably said Ar 1 And Ar is a group 2 Each independently selected from substituted or unsubstituted C10-C14 aryl, substituted or unsubstituted C18-C22 heteroaryl, or triphenylamine groups; ar (Ar) 3 Represents a substituted or unsubstituted C10-C20 aryl, a substituted or unsubstituted C12-C18 heteroaryl or a triphenylamine group; l is a substituted or unsubstituted C6-C30 aryl group; benzene or deuterated benzene is preferred; x represents-O-, -S-, -SO 2 -Si-, -Sn-, or-Ge-; r is R 1 And R is 2 Each independently represents hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, substituted or unsubstitutedSubstituted C1-C30 hydrocarbyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C3-C7 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, -NR 3 R 4 、-SiR 5 R 6 R 7 -、-SR 8 、-OR 9 、-COR 10 、-B(OR 11 )(OR 12 ) The method comprises the steps of carrying out a first treatment on the surface of the Preferably R 1 And R is 2 Hydrogen, methyl or isopropyl; or R is 1 And R is 2 Is linked to adjacent substituents to form a substituted or unsubstituted mono-or polycyclic, in particular a C3-C30 cycloaliphatic or aromatic ring, the carbon atoms of which may be replaced by at least one heteroatom selected from nitrogen, oxygen and sulfur; preferably naphthalene, anthracene or pyrene, or substituted naphthalene, anthracene or pyrene; wherein the substituent is methyl or phenyl; r is R 3 To R 12 Each independently represents a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group; or with adjacent substituents to form a substituted or unsubstituted monocyclic or polycyclic, in particular a C3-C30 aliphatic or aromatic ring; a, b are each integers from 1 to 4; preferably, a and b are 1.
Further preferably, the organic electroluminescent compound is selected from the group consisting of compounds having structures represented by chemical formulas 2 to 4:
Figure BDA0001931112370000161
further preferably, the Ar 1 And Ar is a group 2 Each independently selected from the following structures:
Figure BDA0001931112370000162
the Ar is as follows 3 Selected from the following structures:
Figure BDA0001931112370000171
wherein R is hydrogen, halogen, cyano, C1-C30 alkyl, C6-C50 aryl, C7-C50 aralkyl, C7-C50 arylalkoxy, C7-C50 arylalkylmercapto or C5-C50 heteroaryl; preferably R is hydrogen, benzene, methyl or isopropyl; wherein the alkyl is a straight chain alkyl, branched alkyl, cycloalkyl, a straight chain alkyl substituted with at least 1 substituent, a branched alkyl substituted with at least 1 substituent, or a cycloalkyl substituted with at least 1 substituent; wherein the substituent groups are independently selected from one or more of halogen, cyano, hydroxyl and mercapto. The aryl group is preferably an unsubstituted aryl group or an aryl group substituted with at least 1 substituent; wherein the substituents are independently selected from halogen, amino, cyano, nitro, hydroxy or mercapto; the arylalkyl is preferably unsubstituted arylalkyl or arylalkyl substituted with at least 1 substituent; wherein the substituents are independently selected from halogen, amino, cyano, nitro, hydroxy or mercapto; the arylalkoxy group is preferably an unsubstituted arylalkoxy group or an arylalkoxy group substituted with at least 1 substituent; wherein the substituents are independently selected from halogen, amino, cyano, nitro, hydroxy or mercapto; the arylalkylmercapto group is preferably an unsubstituted arylalkylmercapto group or an arylalkylmercapto group substituted with at least 1 substituent; wherein the substituents are independently selected from halogen, amino, cyano, nitro, hydroxy or mercapto; the heteroaryl is preferably unsubstituted heteroaryl or heteroaryl substituted with at least 1 substituent; wherein the heteroatom in the heteroaryl group is nitrogen, sulfur or oxygen; the substituent groups independently select halogen, amino, cyano, nitro, hydroxyl or sulfhydryl; and the R represents any position of benzene ring where the R is located.
Most preferably, the organic electroluminescent compound is selected from the group consisting of compounds having structures represented by chemical formulas 1 to 135:
Figure BDA0001931112370000191
Figure BDA0001931112370000201
Figure BDA0001931112370000211
Figure BDA0001931112370000221
the invention also provides a preparation method of the organic electroluminescent compound, which comprises the following steps:
step 1, preparation of intermediate 1
Dissolving a compound 2 in tetrahydrofuran, adding n-butyllithium, uniformly stirring, adding the compound 1 dissolved in tetrahydrofuran, and stirring at room temperature for reaction to prepare an intermediate 1;
step 2, preparation of the Compound of chemical formula 1
Dissolving the intermediate 1 and the compound 3 in dichloromethane, then adding boron trifluoride diethyl etherate dissolved in the dichloromethane, and stirring at room temperature for reaction to prepare a compound shown in a chemical formula 1;
the synthetic route is as follows:
Figure BDA0001931112370000222
wherein R is 1 And R is 2 、X、Ar 1 、Ar 2 、Ar 3 L, and a and b are as defined in the above chemical formula 1, and Hal represents halogen.
Preferably, the step 1 specifically includes the following steps: after adding compound 2 and tetrahydrofuran to a reaction vessel, the vessel was cooled to-78 ℃ under nitrogen atmosphere; n-butyllithium was then slowly added dropwise to the foregoing mixture, after stirring the mixture at-78 ℃ for 30 minutes, it was stirred at room temperature for 3 hours, and cooled to-78 ℃; thereafter, compound 1 dissolved in tetrahydrofuran was slowly added dropwise to the mixture; after the addition, the reaction temperature was slowly warmed to room temperature, and the mixture was stirred for 16 hours; then adding an aqueous ammonium chloride solution to the reaction solution to complete the reaction, and extracting the reaction solution with ethyl acetate; the extracted organic layer was then dried using magnesium sulfate and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography to afford intermediate 1.
Preferably, the step 2 specifically includes the following steps: after intermediate 1, compound 3 and methylene chloride were added to the reaction vessel, air was sufficiently replaced with nitrogen three times; boron trifluoride diethyl etherate dissolved in 100mL of dichloromethane was slowly added dropwise to the foregoing mixture; after stirring the mixture at room temperature for 2 hours, it was quenched with distilled water and the mixture was extracted with dichloromethane; the extracted organic layer was then dried over sodium sulfate and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography to obtain a compound represented by chemical formula 1.
The invention also provides an organic electroluminescent device containing the organic electroluminescent compound.
Preferably, the organic electroluminescent device comprises: the electrode comprises a first electrode, a second electrode and an organic matter layer arranged between the two electrodes, wherein the organic matter layer comprises at least one compound with a structure shown in a chemical formula 1; the compound of the structure shown in chemical formula 1 may exist in the organic layer in a single form or mixed with other substances. The above-mentioned materials may contain the organic electroluminescent compound according to the present invention alone, or may further include conventional materials generally used for organic electroluminescent materials. 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 further includes at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron injection layer, a hole blocking layer, and an electron blocking layer.
Example 1: preparation of Compound 1
Figure BDA0001931112370000231
After bromobenzene (60 mmol) and 200mL of tetrahydrofuran were added to the reaction vessel, the vessel was cooled to-78℃under nitrogen atmosphere. N-butyllithium (2.5M, 60 mmol) was then slowly added dropwise to the mixture. After stirring the mixture at-78 ℃ for 30 minutes, it was stirred at room temperature for 3 hours and cooled to-78 ℃. Thereafter, xanthone (60 mmol) dissolved in 200mL of tetrahydrofuran was slowly added dropwise to the mixture. After the addition, the reaction temperature was slowly warmed to room temperature, and the mixture was stirred for 16 hours. Then, an aqueous ammonium chloride solution was added to the reaction solution to complete the reaction, and the reaction solution was extracted with ethyl acetate. The extracted organic layer was then dried over magnesium sulfate and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography to give compound 1-1 (13.15 g, yield 80%, MW: 274.23).
After adding compound 1-1 (45 mmol), triphenylamine (46 mmol) and 500L methylene chloride to the reaction vessel, air was sufficiently replaced with nitrogen three times. Boron trifluoride diethyl etherate (46 mmol) dissolved in 100mL of dichloromethane 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. The extracted organic layer was then dried over sodium sulfate and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography to obtain compound 1 (20.30 g, yield 90%, MW: 501.33).
Example 2: preparation of Compound 11
Figure BDA0001931112370000241
Compound 11 was prepared according to the procedure of example 1 (83% yield, MW: 810.0). The difference from example 1 is that intermediate 1-11 was used instead of intermediate 1-1 and intermediate 2-11 was used instead of intermediate 2-1.
Example 3: preparation of Compound 20
Figure BDA0001931112370000251
Compound 20 was prepared according to the procedure of example 1 (79% yield, MW: 921.11). The difference from example 1 is that intermediate 1-20 was used instead of intermediate 1-1 and intermediate 2-20 was used instead of intermediate 2-1.
Example 4: preparation of Compound 25
Figure BDA0001931112370000252
Compound 25 was prepared according to the procedure for example 1 (83% yield, MW: 818.42). The difference from example 1 is that intermediate 1-25 is used instead of intermediate 1-1 and intermediate 2-25 is used instead of intermediate 2-1.
Example 5: preparation of Compound 33
Figure BDA0001931112370000253
Compound 33 was prepared according to the procedure for example 1 (77% yield, MW: 783.83). The difference from example 1 is that intermediate 1-33 was used instead of intermediate 1-1 and intermediate 2-33 was used instead of intermediate 2-1.
Example 6: preparation of Compound 45
Figure BDA0001931112370000261
Compound 45 was prepared according to the procedure of example 1 (yield 84%, MW: 835.21). The difference from example 1 is that intermediate 1-45 was used instead of intermediate 1-1 and intermediate 2-45 was used instead of intermediate 2-1.
Example 7: preparation of Compound 46
Figure BDA0001931112370000262
Compound 46 (yield 82%, MW: 772.45) was prepared according to the procedure of example 1. The difference from example 1 is that intermediate 1-46 was used instead of intermediate 1-1 and intermediate 2-46 was used instead of intermediate 2-1.
Example 8: preparation of Compound 57
Figure BDA0001931112370000263
Compound 57 was prepared according to the procedure for example 1 (79% yield, MW: 708.81). The difference from example 1 is that intermediate 1-57 is used instead of intermediate 1-1 and intermediate 2-57 is used instead of intermediate 2-1.
Example 9: preparation of Compound 72
Figure BDA0001931112370000271
Compound 72 was prepared according to the procedure for example 1 (84% yield, MW: 733.39). The difference from example 1 is that intermediate 1-72 is used instead of intermediate 1-1 and intermediate 2-72 is used instead of intermediate 2-1.
Example 10: preparation of Compound 103
Figure BDA0001931112370000272
Compound 103 was prepared according to the procedure of example 1 (yield 85%, MW: 867.44). The difference from example 1 is that intermediate 1-103 is used instead of intermediate 1-1 and intermediate 2-103 is used instead of intermediate 2-1.
Example 11: preparation of Compound 107
Figure BDA0001931112370000273
Compound 41 was prepared according to the procedure for example 1 (87% yield, MW: 651.39). The difference from example 1 is that intermediate 1-107 was used instead of intermediate 1-1 and intermediate 2-107 was used instead of intermediate 2-1.
Example 12: manufacture of organic electroluminescent devices containing Compound 1
The thickness of the coating is equal to
Figure BDA0001931112370000274
The ITO glass substrate is washed for 2 times in distilled water for 30 minutes by ultrasonic wave, repeatedly washed for 2 times by distilled water for 10 minutes by ultrasonic wave, and after the distilled water is washed, solvents such as isopropanol, acetone, methanol and the like are washed by ultrasonic wave in sequence, dried and transferred into a plasma washer, and the substrate is washed for 5 minutes and then is sent into a vapor deposition machine. Evaporating 4,4' -tris [ 2-naphthylphenylamino ] with a thickness of 50nm on the prepared ITO transparent electrode]Triphenylamine (2-TNATA) was used as the hole injection layer. Then, the compound 1 was vacuum-evaporated on the formed hole injection layer to form a hole transport layer having a thickness of 30 nm. Then evaporating blue host material 9, 10-bis (2-naphthyl) Anthracene (ADN) with thickness of 30nm and doping material bis (4, 6-difluorophenylpyridine-N, C) on the hole transport layer 2 ) Iridium picolinate (FIrpic). The weight ratio of host material to dopant material was 95:5. Then, TPBi with a thickness of 40nm was vacuum-deposited as a hole blocking layer and an electron transport layer on the light-emitting layer. Lithium fluoride (LiF) having a thickness of 0.5nm was vacuum-deposited on the electron transport layer as an electron injection layer. Finally, aluminum with the thickness of 150nm is evaporated to serve as a cathode, so that the preparation of the organic electroluminescent device is completed. And testing the performance luminescence characteristics of the obtained device, and measuring by using a KEITHLEY 2400 source measuring unit and a CS-2000 spectroradiometer to evaluate the driving voltage, the luminescence brightness and the luminescence efficiency.
Example 13: manufacture of organic electroluminescent devices containing Compound 11
An organic electroluminescent device containing compound 11 was produced in the same manner as in example 12 except that compound 1 was replaced with compound 11.
Example 14: manufacture of organic electroluminescent devices containing Compound 20
An organic electroluminescent device containing compound 20 was produced in the same manner as in example 12 except that compound 1 was replaced with compound 20.
Example 15: manufacture of organic electroluminescent devices containing Compound 25
An organic electroluminescent device containing compound 25 was produced in the same manner as in example 12 except that compound 1 was replaced with compound 25.
Example 16: manufacture of organic electroluminescent devices containing Compound 33
An organic electroluminescent device containing compound 33 was produced in the same manner as in example 12 except that compound 1 was replaced with compound 33.
Example 17: manufacture of organic electroluminescent devices containing Compound 45
An organic electroluminescent device containing compound 45 was produced in the same manner as in example 12 except that compound 1 was replaced with compound 45.
Example 18: manufacture of organic electroluminescent devices containing Compound 46
An organic electroluminescent device containing compound 46 was produced in the same manner as in example 12 except that compound 1 was replaced with compound 46.
Example 19: manufacture of organic electroluminescent devices containing Compound 57
An organic electroluminescent device containing compound 57 was produced in the same manner as in example 12 except that compound 1 was replaced with compound 57.
Example 20: manufacture of organic electroluminescent devices containing compound 72
An organic electroluminescent device containing compound 72 was produced in the same manner as in example 12 except that compound 1 was replaced with compound 72.
Example 21: manufacture of organic electroluminescent devices containing Compound 103
An organic electroluminescent device containing compound 103 was produced in the same manner as in example 12 except that compound 1 was replaced with compound 103.
Example 22: manufacture of organic electroluminescent devices containing Compound 107
An organic electroluminescent device containing compound 107 was produced in the same manner as in example 12 except that compound 1 was replaced with compound 107.
Example 23: manufacture of NPD-containing organic electroluminescent devices
An organic electroluminescent device containing NPD was fabricated by replacing the material of the hole transport layer with N '-bis (1-naphthyl) -N, N' -diphenyl- (1, 1 '-biphenyl) -4,4' -diamine (NPD) from compound 1 in the same manner as in example 12.
Table 1 shows the results of the luminescence characteristics of the compounds prepared in the examples of the present invention and the organic electroluminescent devices prepared by NPD.
TABLE 1
Figure BDA0001931112370000301
From the above table, it can be seen that the compounds provided by the present invention have suitable glass transition temperatures, and that the luminous efficiency and lifetime of devices made from the compounds of the present invention as hole transport layers are significantly improved over devices made from NPD as hole transport layers.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.

Claims (5)

1. An organic electroluminescent compound, characterized in that it is selected from one of the compounds of the following chemical formula:
Figure FDA0004041948080000011
2. the method for producing an organic electroluminescent compound according to claim 1, comprising the steps of:
step 1, preparation of intermediate 1
Dissolving a compound 2 in tetrahydrofuran, adding n-butyllithium, uniformly stirring, adding the compound 1 dissolved in tetrahydrofuran, and stirring at room temperature for reaction to prepare an intermediate 1;
step 2, preparation of the Compound of chemical formula 1
Dissolving the intermediate 1 and the compound 3 in dichloromethane, then adding boron trifluoride diethyl etherate dissolved in the dichloromethane, and stirring at room temperature for reaction to prepare a compound shown in a chemical formula 1;
the synthetic route is as follows:
Figure FDA0004041948080000021
wherein Hal represents halogen and the remaining substituents and numbers correspond to the substituents and numbers on the individual compounds of claim 1.
3. The method for preparing an organic electroluminescent compound according to claim 2, wherein the step 1 comprises the steps of:
after adding compound 2 and tetrahydrofuran to a reaction vessel, the vessel was cooled to-78 ℃ under nitrogen atmosphere; n-butyllithium was then added dropwise to the foregoing mixture, after stirring the mixture at-78 ℃ for 30 minutes, it was stirred at room temperature for 3 hours, and cooled to-78 ℃; thereafter, compound 1 dissolved in tetrahydrofuran was added dropwise to the mixture; after the addition, the reaction temperature was allowed to warm to room temperature, and the mixture was stirred for 16 hours; then adding an aqueous ammonium chloride solution to the reaction solution to complete the reaction, and extracting the reaction solution with ethyl acetate; the extracted organic layer was then dried using magnesium sulfate and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography to afford intermediate 1.
4. The method for preparing an organic electroluminescent compound according to claim 2, wherein the step 2 comprises the steps of:
after intermediate 1, compound 3 and methylene chloride were added to the reaction vessel, air was sufficiently replaced with nitrogen three times; boron trifluoride diethyl etherate dissolved in 100mL of dichloromethane was added dropwise to the foregoing mixture; after stirring the mixture at room temperature for 2 hours, it was quenched with distilled water and the mixture was extracted with dichloromethane; the extracted organic layer was then dried over sodium sulfate and the solvent was removed using a rotary evaporator; the remaining material was purified by column chromatography to obtain a compound represented by chemical formula 1.
5. An organic electroluminescent device comprising the organic electroluminescent compound as claimed in claim 1.
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