CN112979623A - Five-membered heterocyclic compound, preparation method thereof, organic electroluminescent device and element - Google Patents

Five-membered heterocyclic compound, preparation method thereof, organic electroluminescent device and element Download PDF

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CN112979623A
CN112979623A CN202110196451.7A CN202110196451A CN112979623A CN 112979623 A CN112979623 A CN 112979623A CN 202110196451 A CN202110196451 A CN 202110196451A CN 112979623 A CN112979623 A CN 112979623A
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CN112979623B (en
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马晓宇
徐佳楠
金成寿
贾宇
汪康
陈振生
韩文坤
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The invention provides a five-membered heterocyclic compound, a preparation method thereof, an organic electroluminescent device and an element. The five-membered heterocyclic compound provided by the invention contains a five-membered heterocyclic core, is connected with a rigid functional group, breaks through the structural limitation of arylamines of the traditional CPL material, ensures the high overlapping of electron clouds of HOMO (highest occupied molecular orbital) and LUMO (Low occupied molecular orbital) due to stronger electron-withdrawing capability and more regular symmetry, has very high polarizability and refractive index, and also has higher glass transition temperature and molecular thermal stability, and can effectively improve the light extraction efficiency of an OLED (organic light emitting diode) device, reduce the driving voltage of the device, improve the luminous efficiency and the brightness of the device and prolong the service life of the device after being applied to a CPL layer of the OLED device. The five-membered heterocyclic compound provided by the invention can also be used as a hole blocking layer or an electron transport layer of an OLED device, and can effectively improve the recombination efficiency of holes and electrons in a light-emitting layer, thereby improving the light-emitting efficiency and prolonging the service life of the device.

Description

Five-membered heterocyclic compound, preparation method thereof, organic electroluminescent device and element
Technical Field
The invention relates to the technical field of semiconductors, in particular to a five-membered heterocyclic compound, a preparation method thereof, an organic electroluminescent device and an element.
Background
As a novel flat panel Display, an Organic Light Emitting Display (OLED for short) has the advantages of thinness, lightness, wide viewing angle, active Light emission, continuously adjustable Light emission color, low cost, high response speed, low energy consumption, low driving voltage, wide working temperature range, simple production process, high Light Emitting efficiency, flexible Display and the like, compared with a Liquid Crystal Display (LCD for short).
Until now, many improvements have been made for practical use of organic EL elements, and various functions have been subdivided, and an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are provided in this order according to the function on a substrate. In organic electroluminescent devices, high efficiency and durability have been achieved by a light emitting element of a bottom emission structure that emits light from the bottom.
In recent years, a light emitting element of a top emission structure which emits light from above using a metal having a high work function as an anode has been started. In the light emitting element having the top emission structure, a translucent electrode such as LiF/Al/Ag, Ca/Mg, LiF/MgAg, or the like is used as a cathode. In such a light-emitting element, when light emitted from the light-emitting layer enters another film, the light is totally reflected at the interface between the light-emitting layer and the other film when the light enters at a certain angle or more. Therefore, only a part of the emitted light can be utilized. In order to improve the light extraction efficiency, it has been proposed to provide a cap layer having a high refractive index outside the translucent electrode having a low refractive index to adjust the optical interference distance, suppress external light reflection, and suppress extinction due to movement of surface plasmon, thereby improving the light extraction efficiency and improving the light emission efficiency.
The light extraction efficiency is improved to some extent as a coating layer for adjusting the refractive index. However, the refractive index of the existing CPL material (i.e. cap layer material) is generally below 1.9, which cannot meet the requirement of high refractive index, and the light emitting efficiency is low. In order to improve the characteristics of organic EL elements, particularly to greatly improve the light extraction efficiency, it is necessary to develop a material having a high refractive index to improve the light extraction efficiency and solve the problem of light emission efficiency.
Disclosure of Invention
In view of the above, the present invention provides a five-membered heterocyclic compound, a method for preparing the same, an organic electroluminescent device and an element. The five-membered heterocyclic compound provided by the invention can effectively reduce the driving voltage of an organic electroluminescent device, improve the luminous efficiency and brightness of the device and prolong the service life of the device.
The invention provides a five-membered heterocyclic compound, which has a structure shown in a formula I:
Figure BDA0002946895790000021
wherein:
x is selected from: -O-, -S-, -C (R)15)(R16) -or-N (R)17)-；
X1、X2Independently selected from: c or N;
R1、R2independently selected from: C1-C20 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 5-to 30-membered heteroaryl;
R15、R16、R17independently selected from: C1-C10 alkyl, C1-C10 alkoxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted 5-60 membered heteroaryl; or R15And R16Bonding to form a ring;
L1、L2independently selected from: single bond, C1-C10 alkyl, halogen, protium, deuterium, tritium, C1-C10 alkyl substituted or unsubstituted phenyl, naphthyl, biphenyl, terphenyl, anthracenyl, pyridyl;
Ar1、Ar2independently selected from the structures shown in formulas II-IV:
Figure BDA0002946895790000022
in formula II:
R3、R4、R5、R6independently selected from: a connecting bond, a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a substituted or unsubstituted C1-C6 chain alkyl group, a substituted or unsubstituted C5-C10 cycloalkyl group, a substituted or unsubstituted C2-C6 chain alkenyl group, a substituted or unsubstituted C1-C6 chain alkoxy group, a substituted or unsubstituted C5-C10 cycloalkoxy group, a substituted or unsubstituted aromatic hydrocarbon group, a C1-C10 alkyl-substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, a substituted or unsubstituted aryloxy group;
Y1、Y2、Y3independently selected from: carbon atom, oxygen atomSulfur atom or nitrogen atom; wherein the number of oxygen atoms is not more than 1, and the number of sulfur atoms is not more than 1;
Ar3、Ar4、Ar5independently selected from: a connecting bond, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group;
wherein R is3、R4、R5、R6、Ar3、Ar4And Ar51 of them is a connecting bond;
in formula III:
R7、R8、R9independently selected from: a connecting bond, C1-C10 chain alkyl, halogen, protium, deuterium, tritium, C1-C10 alkyl substituted or unsubstituted phenyl, naphthyl, biphenylyl, terphenyl, anthracenyl, pyridyl, dibenzofuranyl, dibenzothiazolyl, 9-dimethylfluorene, N-phenylcarbazole; and R is7、R8And R91 of them is a connecting bond;
Z1、Z2、Z3independently selected from: a carbon atom or a nitrogen atom;
in formula IV:
R10、R11、R12、R13、R14independently selected from: a connecting bond, a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a substituted or unsubstituted C1-C6 chain alkyl group, a substituted or unsubstituted C5-C10 cycloalkyl group, a substituted or unsubstituted C2-C6 chain alkenyl group, a substituted or unsubstituted C1-C6 chain alkoxy group, a substituted or unsubstituted C5-C10 cycloalkoxy group, a substituted or unsubstituted aromatic hydrocarbon group, a C1-C10 alkyl-substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, a substituted or unsubstituted aryloxy group; and R is10、R11、R12、R13And R141 of them is a connecting bond;
A1、A2、A3、A4independently selected from: carbon atoms or nitrogen atoms.
Preferably, the first and second liquid crystal materials are,
the R is1、R2The method comprises the following steps:
in the substituted or unsubstituted C6-C30 aryl and the substituted or unsubstituted 5-to 30-membered heteroaryl, the substituent is selected from: protium, deuterium, tritium, halogen, cyano, C1-C20 alkyl, C1-C20 alkoxy, C6-C20 aryl, 5-20 membered heteroaryl;
in the substituted or unsubstituted 5-30-membered heteroaryl, the heteroatom of the heteroaryl is selected from the group consisting of: nitrogen, oxygen or sulfur;
the R is15、R16、R17The method comprises the following steps:
in the substituted or unsubstituted C6-C60 aryl and the substituted or unsubstituted 5-60-membered heteroaryl, the substituent is selected from the following groups: protium, deuterium, tritium, halogen, cyano, C1-C20 alkyl, C1-C20 alkoxy, C6-C20 aryl, 5-20 membered heteroaryl;
in the substituted or unsubstituted 5-60-membered heteroaryl, the heteroatom of the heteroaryl is selected from the group consisting of: nitrogen, oxygen or sulfur;
the R is3、R4、R5、R6The method comprises the following steps:
in the formula III, Z1、Z2、Z3When all are nitrogen atoms, in the formula I, Ar1、Ar2At most 1 of them is the structure shown in formula III.
Preferably, selected from the following structures:
Figure BDA0002946895790000041
Figure BDA0002946895790000051
Figure BDA0002946895790000061
Figure BDA0002946895790000071
the invention also provides a preparation method of the five-membered heterocyclic compound in the technical scheme, which comprises the following steps:
reacting the reactant A, the reactant B and the reactant C to obtain a compound shown as a formula I;
Figure BDA0002946895790000081
preferably, the reaction temperature is 80-120 ℃.
Preferably, Ar is1≠Ar2And/or L1≠L2The preparation method comprises the following steps:
a) reacting reactant A with reactant B to form intermediate D;
b) reacting the intermediate D with a reactant C to form a compound shown as a formula I;
Figure BDA0002946895790000082
or
Ar1＝Ar2And L is1＝L2The preparation method comprises the following steps: reacting the reactant A with the reactant B to form the compound shown in the formula I.
The invention also provides an organic electroluminescent device, wherein at least one functional layer of the organic electroluminescent device contains the five-membered heterocyclic compound in the technical scheme.
Preferably, the CPL layer of the organic electroluminescent device contains the five-membered heterocyclic compound described in the above technical scheme.
Preferably, the hole blocking layer and/or the electron transport layer of the organic electroluminescent device contain the five-membered heterocyclic compound described in the above technical scheme.
The invention also provides an element, which is a lighting or display element; the element comprises the organic electroluminescent device in the technical scheme.
The five-membered heterocyclic compound provided by the invention contains a five-membered heterocyclic core, is connected with a rigid functional group, breaks through the structural limitation of arylamines of the traditional CPL material (namely a cathode cap layer material), ensures the high overlapping of electron clouds of HOMO (highest occupied molecular orbital) and LUMO (LUMO) orbitals due to the strong electron-withdrawing capability and the more regular symmetry, has very high polarizability and refractive index, and also has higher glass transition temperature and molecular thermal stability. In addition, the five-membered heterocyclic compound structure provided by the invention has stronger electron-withdrawing capability and high electron mobility, can be used as a hole blocking layer or an electron transport layer of an OLED device, and can effectively improve the recombination efficiency of holes and electrons in a light-emitting layer, thereby improving the light-emitting efficiency and prolonging the service life of the device.
Experimental results show that the five-membered heterocyclic compound provided by the invention has a refractive index of more than or equal to 2.0, a glass transition temperature Tg of more than or equal to 150 ℃ and higher refractive index and stability for visible light with a wavelength of 450-635 nm. In addition, the five-membered heterocyclic compound provided by the invention enables the driving voltage of the organic electroluminescent device to be below 4.0V, the current efficiency to reach above 43cd/A, and the service life to be obviously improved.
Detailed Description
The invention provides a five-membered heterocyclic compound, which has a structure shown in a formula I:
Figure BDA0002946895790000091
in formula I:
x is selected from: -O-, -S-, -C (R)15)(R16) -or-N (R)17)-；
Wherein the content of the first and second substances,
R15、R16、R17independently selected from: C1-C10 alkyl, C1-C10 alkoxy, substituted or unsubstitutedC6-C60 aryl, substituted or unsubstituted 5-60 membered heteroaryl; or R15And R16Bonded to form a ring.
Preferably:
in the substituted or unsubstituted C6-C60 aryl and the substituted or unsubstituted 5-to 60-membered heteroaryl, the substituent is selected from: protium, deuterium, tritium, halogen, cyano, C1-C20 alkyl, C1-C20 alkoxy, C6-C20 aryl, 5-20 membered heteroaryl.
In the substituted or unsubstituted 5-60-membered heteroaryl, the heteroatom of the heteroaryl is selected from the group consisting of: nitrogen, oxygen or sulfur. The hetero atom in the heteroaryl group is 1 or more.
In formula I:
X1、X2independently selected from: c or N.
R1、R2Independently selected from: C1-C20 alkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted 5-to 30-membered heteroaryl.
Preferably, R1、R2The method comprises the following steps:
in the substituted or unsubstituted C6-C30 aryl and the substituted or unsubstituted 5-to 30-membered heteroaryl, the substituent is selected from: protium, deuterium, tritium, halogen, cyano, C1-C20 alkyl, C1-C20 alkoxy, C6-C20 aryl, 5-20 membered heteroaryl.
In the substituted or unsubstituted 5-30-membered heteroaryl, the heteroatom of the heteroaryl is selected from the group consisting of: nitrogen, oxygen or sulfur. The hetero atom in the heteroaryl group is 1 or more.
In formula I:
L1、L2independently selected from: single bond, C1-C10 alkyl, halogen, protium, deuterium, tritium, C1-C10 alkyl substituted or unsubstituted phenyl, naphthyl, biphenyl, terphenyl, anthracenyl, pyridyl. L is1And L2May be the same or different.
In formula I:
Ar1、Ar2independently selected from the structures shown in formulas II-IV:
Figure BDA0002946895790000101
in formula II:
R3、R4、R5、R6independently selected from: a connecting bond, a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a substituted or unsubstituted C1-C6 chain alkyl group, a substituted or unsubstituted C5-C10 cycloalkyl group, a substituted or unsubstituted C2-C6 chain alkenyl group, a substituted or unsubstituted C1-C6 chain alkoxy group, a substituted or unsubstituted C5-C10 cycloalkoxy group, a substituted or unsubstituted aromatic hydrocarbon group, a C1-C10 alkyl-substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, a substituted or unsubstituted aryloxy group;
wherein the chain alkyl is a straight chain alkyl or a branched chain alkyl. The chain alkenyl group is a straight chain alkenyl group or a branched chain alkenyl group.
Y1、Y2、Y3Independently selected from: a carbon atom, an oxygen atom, a sulfur atom or a nitrogen atom; wherein the number of oxygen atoms is not more than 1 and the number of sulfur atoms is not more than 1.
Ar3、Ar4、Ar5Independently selected from: a connecting bond, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group.
Wherein R is3、R4、R5、R6、Ar3、Ar4And Ar51 of them is a connecting bond; preferably, R4、Ar3、Ar4And Ar51 of them is a connecting bond. The connecting bond is a single bond.
More preferably, formula ii is selected from the following structures:
Figure BDA0002946895790000111
wherein the asterisk indicates the attachment position.
In formula III:
R7、R8、R9independently selected from: a connecting bond, C1-C10 chain alkyl, halogen, protium, deuterium, tritium, C1-C10 alkyl substituted or unsubstituted phenyl, naphthyl, biphenylyl, terphenyl, anthracenyl, pyridyl, dibenzofuranyl, dibenzothiazolyl, 9-dimethylfluorene, N-phenylcarbazole; and R is7、R8And R91 of them is a connecting bond; the connecting bond is a single bond.
Z1、Z2、Z3Independently selected from: carbon atoms or nitrogen atoms.
Wherein Z is1、Z2、Z3When all are nitrogen atoms, in the formula I, Ar1、Ar2At most 1 of them is the structure shown in formula III.
More preferably, formula iii is selected from the following structures:
Figure BDA0002946895790000112
Figure BDA0002946895790000121
wherein the asterisk indicates the attachment position.
In formula IV:
R10、R11、R12、R13、R14independently selected from: a connecting bond, a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a substituted or unsubstituted C1-C6 chain alkyl group, a substituted or unsubstituted C5-C10 cycloalkyl group, a substituted or unsubstituted C2-C6 chain alkenyl group, a substituted or unsubstituted C1-C6 chain alkoxy group, a substituted or unsubstituted C5-C10 cycloalkoxy group, a substituted or unsubstituted aromatic hydrocarbon group, a C1-C10 alkyl-substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group, a substituted or unsubstituted aryloxy group; and R is10、R11、R12、R13And R141 of them being a connecting bond, preferably, R10Or R11Is a connecting bond. The connecting bond is a single bond.
Wherein the chain alkyl is a straight chain alkyl or a branched chain alkyl. The chain alkenyl group is a straight chain alkenyl group or a branched chain alkenyl group.
A1、A2、A3、A4Independently selected from: carbon atoms or nitrogen atoms.
More preferably, formula iv is selected from the following structures:
Figure BDA0002946895790000122
wherein the asterisk indicates the attachment position.
More preferably, the five-membered heterocyclic compound provided by the present invention is selected from the following structures:
Figure BDA0002946895790000131
Figure BDA0002946895790000141
Figure BDA0002946895790000151
Figure BDA0002946895790000161
in the above structure, D represents tritium.
The refractive index of the five-membered heterocyclic compound provided by the invention is more than or equal to 2.0 for visible light with the wavelength of 450-635 nm.
The five-membered heterocyclic compound provided by the invention contains a five-membered heterocyclic core, is connected with a rigid functional group, breaks through the structural limitation of arylamines of the traditional CPL material (namely a cathode cap layer material), ensures the high overlapping of electron clouds of HOMO (HOMO molecular orbital) and LUMO (LUMO) orbitals due to the strong electron-withdrawing capability and the more regular symmetry, has very high polarizability and refractive index, and also has higher glass transition temperature and molecular thermal stability. In addition, the five-membered heterocyclic compound structure provided by the invention has stronger electron-withdrawing capability and high electron mobility, can be used as a hole blocking layer or an electron transport layer of an OLED device, and can effectively improve the recombination efficiency of holes and electrons in a light-emitting layer, thereby improving the light-emitting efficiency and prolonging the service life of the device. The five-membered heterocyclic compound provided by the invention has good application effect and industrialization prospect in OLED devices.
Experimental results show that the five-membered heterocyclic compound provided by the invention has a refractive index of more than or equal to 2.0, a glass transition temperature Tg of more than or equal to 150 ℃ and higher refractive index and stability for visible light with a wavelength of 450-635 nm. In addition, the five-membered heterocyclic compound provided by the invention enables the driving voltage of the organic electroluminescent device to be below 4.0V, the current efficiency to reach above 43cd/A, and the service life to be obviously improved.
The invention also provides a preparation method of the five-membered heterocyclic compound in the technical scheme, which is characterized by comprising the following steps:
reacting the reactant A, the reactant B and the reactant C to obtain a compound shown as a formula I;
Figure BDA0002946895790000171
wherein, X, X1、X2、R1、R2、L1、L2、Ar1、Ar2The types of the above-mentioned components are the same as those in the above-mentioned technical solution, and are not described in detail herein.
In the invention, the reaction temperature is preferably 80-120 ℃.
In the invention, the preparation method comprises two modes according to different groups in reactants, and comprises the following steps:
(1)Ar1≠Ar2and/or L1≠L2The preparation method comprises the following steps:
a) reacting reactant A with reactant B to form intermediate D;
b) reacting the intermediate D with a reactant C to form a compound shown as a formula I;
Figure BDA0002946895790000181
with respect to step a):
the reaction is preferably carried out in the presence of a catalyst and a basic substance. Wherein, the catalyst is preferably Pd (PPh)3)4And/or Pd2(dpa)3More preferably Pd (PPh)3)4. The basic substance is preferably potassium carbonate. The molar ratio of the catalyst to the basic substance to the reactant B is preferably (0.001-0.05): (1-4): 1.
The reaction is preferably carried out in a solvent medium. The solvent is preferably one or more of toluene, ethanol and water; more preferably a mixture of toluene, ethanol and water. Wherein the dosage ratio of the solvent to the reactant B is preferably (30-70) mmol to (200-400) mL.
The reaction is preferably carried out under a protective gas atmosphere. The protective gas used in the present invention is not particularly limited, and may be any conventional inert gas known to those skilled in the art, such as nitrogen or argon.
The reaction temperature is preferably 80-120 ℃, and more preferably 90 ℃; the reaction time is preferably 10-30 h. After the reaction, the intermediate D is obtained by cooling and purifying through a silica gel column.
With respect to step b):
the reaction is preferably carried out in the presence of a catalyst and a basic substance. Wherein, the catalyst is preferably Pd (PPh)3)4And/or Pd2(dpa)3More preferably Pd (PPh)3)4. The basic substance is preferably potassium carbonate. The molar ratio of the catalyst to the basic substance to the reactant C is preferably (0.001-0.05): (1-4): 1.
The reaction is preferably carried out in a solvent medium. The solvent is preferably one or more of toluene, ethanol and water; more preferably a mixture of toluene, ethanol and water. Wherein the dosage ratio of the solvent to the reactant C is preferably (30-70) mmol to (200-400) mL.
The reaction is preferably carried out under a protective gas atmosphere. The protective gas used in the present invention is not particularly limited, and may be any conventional inert gas known to those skilled in the art, such as nitrogen or argon.
The reaction temperature is preferably 80-120 ℃, and more preferably 90 ℃; the reaction time is preferably 10-30 h. After the reaction, cooling and purifying by a silica gel column to obtain the compound shown in the formula I.
(2)Ar1＝Ar2And L is1＝L2The preparation method comprises the following steps: reacting the reactant A with the reactant B to form the compound shown in the formula I.
The reaction is preferably carried out in the presence of a catalyst and a basic substance. Wherein, the catalyst is preferably Pd (PPh)3)4And/or Pd2(dpa)3More preferably Pd (PPh)3)4. The basic substance is preferably potassium carbonate. The molar ratio of the catalyst to the basic substance to the reactant B is preferably (0.001-0.05): (1-4): 1.
The reaction is preferably carried out in a solvent medium. The solvent is preferably one or more of toluene, ethanol and water; more preferably a mixture of toluene, ethanol and water. Wherein the dosage ratio of the solvent to the reactant B is preferably (30-70) mmol to (200-400) mL.
The reaction is preferably carried out under a protective gas atmosphere. The protective gas used in the present invention is not particularly limited, and may be any conventional inert gas known to those skilled in the art, such as nitrogen or argon.
The reaction temperature is preferably 80-120 ℃, and more preferably 90 ℃; the reaction time is preferably 10-30 h. After the reaction, cooling and purifying by a silica gel column to obtain the compound shown in the formula I.
In the two preparation methods provided by the invention, coupling reaction between boric acid (from reactant A and reactant C) and halogen atom (from reactant B) is mainly utilized in the reaction process, the dosage of each reactant is equivalent in one coupling reaction, and when multiple coupling reactions (such as the method 1) exist, the structure of the reactant is changed according to one coupling reaction and one substitution reaction is repeated.
The preparation method provided by the invention is simple and feasible, and is suitable for large-scale production.
The invention also provides an organic electroluminescent device, wherein at least one functional layer of the organic electroluminescent device contains the five-membered heterocyclic compound in the technical scheme.
In the invention, the organic electroluminescent device comprises a cathode, an anode, one or more functional layers arranged between the cathode and the anode, and a cathode cap layer (namely a CPL layer) covering the cathode. Preferably, the functional layer includes at least one of a hole injection layer, a hole transport layer, a light emission auxiliary layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.
In the present invention, preferably, the CPL layer of the organic electroluminescent device contains the five-membered heterocyclic compound described in the above technical solution.
In the present invention, it is preferable that the hole blocking layer and/or the electron transport layer of the organic electroluminescent device contain the five-membered heterocyclic compound described in the above technical solution.
The invention also provides an element, which is a lighting or display element; the element comprises the organic electroluminescent device in the technical scheme.
At least one functional layer in the organic electroluminescent device provided by the invention contains the five-membered heterocyclic compound in the technical scheme, the five-membered heterocyclic compound contains a five-membered heterocyclic core and is connected with a rigid functional group, the aromatic amine structural limitation of the traditional CPL material (namely a cathode cap layer material) is broken through, the electronic cloud height overlapping of HOMO (HOMO-material atomic emission) orbitals and LUMO (LUMO) orbitals is ensured due to the strong electron-withdrawing capability and the more regular symmetry, the polarization rate and the refractive index are very high, the glass transition temperature and the molecular thermal stability are higher, and after the organic electroluminescent device is applied to the CPL layer of the OLED device, the light extraction efficiency of the OLED device can be effectively improved, the driving voltage of the device is reduced, the luminous efficiency and the brightness of the device are improved. In addition, the five-membered heterocyclic compound structure provided by the invention has stronger electron-withdrawing capability and high electron mobility, can be used as a hole blocking layer or an electron transport layer of an OLED device, and can effectively improve the recombination efficiency of holes and electrons in a light-emitting layer, thereby improving the light-emitting efficiency and prolonging the service life of the device.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1: synthesis of Compound 1
The synthetic route is as follows:
Figure BDA0002946895790000201
the synthesis process is as follows:
pd (pph)3)4(0.5mmol), potassium carbonate (100mmol), a reactant A-1(110mmol) and a reactant B-1(50mmol) are added into a reaction bottle, 300mL of mixed solution of toluene, ethanol and water is added (the volume ratio of the toluene, the ethanol and the water is 150: 75), nitrogen is used for protection, and the temperature is raised to 90 ℃ for reaction for 24 hours. After cooling, a white powder was precipitated, which was filtered to obtain a white solid, which was dissolved in methylene chloride and passed through a silica gel funnel to obtain the compound 1(27.82g, yield: 92%, HPLC purity > 99.9%).
The detection analysis of the obtained compound 1 was carried out, and the results were as follows:
testing by mass spectrometry: a theoretical value of 604.71; the test value was 604.25.
Elemental analysis:
the theoretical values are: c, 83.42; h, 4.67; n, 9.27; o, 2.65;
the test values are: c, 83.40; h, 4.68; n, 9.29; o, 2.65.
Example 2: synthesis of Compound 23
The synthetic route is as follows:
Figure BDA0002946895790000202
the synthesis process is as follows:
pd (pph)3)4(0.5mmol), potassium carbonate (100mmol), reactant A-23(110mmol) and reactant B-23(50mmol) were charged into a reaction flask, and 300mL of a mixture of toluene, ethanol and water (volume ratio of toluene, ethanol and water as in example 1) were added thereto, and the mixture was heated to 90 ℃ under nitrogen protection for 24 hours. After cooling, a white powder was precipitated, which was filtered to obtain a white solid, which was dissolved in methylene chloride and passed through a silica gel funnel to obtain the compound 23(35.94g, yield: 93%, HPLC purity > 99.9%).
The compound 23 obtained was subjected to detection analysis, and the results were as follows:
testing by mass spectrometry: a theoretical value of 772.97; the test value was 772.56.
Elemental analysis:
the theoretical values are: c, 83.91; h, 4.69; n, 7.25; s, 4.15;
the test values are: c, 83.88; h, 4.70; n, 7.22; and S, 4.14.
Example 3: synthesis of Compound 25
The synthetic route is as follows:
Figure BDA0002946895790000211
the synthesis process is as follows:
pd (pph)3)4(0.5mmol), potassium carbonate (100mmol), transA reactant A-25(110mmol) and a reactant B-25(50mmol) were added to a reaction flask, and 300mL of a mixture of toluene, ethanol and water (the volume ratio of toluene, ethanol and water was the same as in example 1) were added thereto, and the mixture was heated to 90 ℃ under nitrogen protection for 24 hours. After cooling, a white powder was precipitated, which was filtered to obtain a white solid, which was dissolved in methylene chloride and passed through a silica gel funnel to obtain the compound 25(30.82g, yield: 95%, HPLC purity > 99.9%).
The compound 25 thus obtained was subjected to detection analysis, and the results were as follows:
testing by mass spectrometry: a theoretical value of 648.83; the test value was 648.71.
Elemental analysis:
the theoretical values are: c, 81.45; h, 4.97; n, 8.64; s, 4.94;
the test values are: c, 81.43; h, 4.98; n, 8.64; and S, 4.96.
Example 4: synthesis of Compound 29
The synthetic route is as follows:
Figure BDA0002946895790000221
the synthesis process is as follows:
pd (pph)3)4(0.5mmol), potassium carbonate (100mmol), reactant A-29(110mmol) and reactant B-29(50mmol) were charged into a reaction flask, and 300mL of a mixture of toluene, ethanol and water (volume ratio of toluene, ethanol and water as in example 1) were added thereto, and the mixture was heated to 90 ℃ under nitrogen protection for 24 hours. After cooling, a white powder was precipitated, which was filtered to obtain a white solid, which was dissolved in methylene chloride and passed through a silica gel funnel to obtain the compound 29(27.71g, yield: 89%, HPLC purity > 99.9%).
The compound 29 thus obtained was subjected to assay, and the results were as follows:
testing by mass spectrometry: a theoretical value of 622.75; the test value was 622.60.
Elemental analysis:
the theoretical values are: c, 77.15; h, 4.21; n, 13.50; s, 5.15;
the test values are: c, 77.13; h, 4.22; n, 13.51; and S, 5.16.
Example 5: synthesis of Compound 40
The synthetic route is as follows:
Figure BDA0002946895790000222
the synthesis process is as follows:
s1, synthesis of intermediate C-40:
after the addition of reactant A-40(55mmol) and reactant B-40(50mmol) to the reaction vessel, Pd (PPh) was added3)4(0.5mmol), potassium carbonate (100mmol), and 300mL of a mixture of solvents toluene, ethanol and water (volume ratio of toluene, ethanol and water as in example 1), and the air was sufficiently replaced with nitrogen three times; the temperature was raised to 90 ℃ and the reaction was carried out for about 18 hours. After the reaction is finished, the temperature is reduced, liquid separation is carried out, the organic solvent is dried in a spinning mode, a white solid is obtained, the white solid is dissolved by dichloromethane of about 30mL, then the white solid passes through a silica gel column, most of products are washed out by dichloromethane and petroleum ether of 1: 3, and a white intermediate C-40(44mmol) is obtained after the drying in a spinning mode.
S2, synthesis of compound 40:
pd is added2(dpa)3(1.2mmol), potassium carbonate (80mmol), intermediate C-40(44mmol) and reactant D-40(40mmol) were added to a reaction flask, 300mL of a mixture of toluene, ethanol and water (volume ratio of toluene, ethanol and water as in example 1) were added thereto, and the mixture was heated to 90 ℃ under nitrogen protection for 24 hours. After cooling, a white powder was precipitated, which was filtered to obtain a white solid, which was dissolved in methylene chloride and passed through a silica gel funnel to obtain the compound (40) (26.03g, yield: 85%, HPLC purity > 99.9%).
The compound 40 obtained was subjected to detection analysis, and the results were as follows:
testing by mass spectrometry: a theoretical value of 696.23; the test value was 696.11.
Elemental analysis:
the theoretical values are: c, 82.73; h, 4.63; n, 8.04; s, 4.60;
the test values are: c, 82.71; h, 4.64; n, 8.05; and S, 4.60.
Example 6: synthesis of Compound 49
The synthetic route is as follows:
Figure BDA0002946895790000231
the synthesis process is as follows:
pd (pph)3)4(0.5mmol), potassium carbonate (100mmol), reactant A-49(4- (benzoxazol-2-yl) phenylboronic acid, 110mmol) and reactant B-29(2, 5-dibromofuran, 50mmol) were charged into a reaction flask, and 300mL of a mixture of toluene, ethanol and water (volume ratio of toluene, ethanol and water as in example 1) were added thereto, and the mixture was heated to 90 ℃ under nitrogen protection for 24 hours. After cooling, a white powder was precipitated, which was filtered to obtain a white solid, which was dissolved in methylene chloride and passed through a silica gel funnel to obtain the compound 49(21.88g, yield: 93%, HPLC purity > 99.9%).
The compound 49 thus obtained was subjected to detection analysis, and the results were as follows:
testing by mass spectrometry: a theoretical value of 470.55; the test value was 470.23.
Elemental analysis:
the theoretical values are: c, 76.58; h, 3.86; n, 5.95; o, 6.80; s, 6.81;
the test values are: c, 76.57; h, 3.87; n, 5.93; o, 6.81; and S, 6.82.
Example 7: synthesis of Compound 58
The synthetic route is as follows:
Figure BDA0002946895790000241
the synthesis process is as follows:
pd (pph)3)4(0.5mmol), potassium carbonate (100mmol), reactant A-58(110mmol) and reactant B-58(50mmol) were charged into a reaction flask, and 300mL of a mixture of toluene, ethanol and water (volume ratio of toluene, ethanol and water as in example 1) were added thereto, and the mixture was heated to 90 ℃ under nitrogen protection for 24 hours. Cooling and separating outA white powder was obtained, which was filtered off with suction to give a white solid, which was dissolved in dichloromethane and passed through a silica gel funnel to give the indicated compound 58(28.6465g, yield: 92%, HPLC purity > 99.9%).
The compound 29 thus obtained was subjected to assay, and the results were as follows:
testing by mass spectrometry: a theoretical value of 622.75; the test value was 622.31.
Elemental analysis:
the theoretical values are: c, 77.15; h, 4.21; n, 13.50; s, 5.15;
the test values are: c, 77.13; h, 4.22; n, 13.50; and S, 5.16.
Example 8: synthesis of Compound 60
The synthetic route is as follows:
Figure BDA0002946895790000242
the synthesis process is as follows:
s1, synthesis of intermediate C-60:
after the addition of reactant A-60(55mmol) and reactant B-60(50mmol) to the reaction vessel, Pd (PPh) was added3)4(0.5mmol), potassium carbonate (100mmol), and 300mL of a mixture of solvents toluene, ethanol and water (volume ratio of toluene, ethanol and water as in example 1), and the air was sufficiently replaced with nitrogen three times; the temperature was raised to 90 ℃ and the reaction was carried out for about 18 hours. And after the reaction is finished, cooling, separating liquid, spin-drying the organic solvent to obtain a white solid, dissolving the white solid by using dichloromethane about 30mL, and then passing through a silica gel column, wherein dichloromethane: petroleum ether is 1: 3 most of the product is flushed out, and after spin-drying, the white intermediate C-60(46mmol) is obtained.
S2, synthesis of compound 60:
pd (PPh)3)4(0.4mmol), potassium carbonate (80mmol), intermediate C-60(45mmol) and reactant D-60(5 '-phenyl [1,1':3', 1' -terphenyl)]-4-yl) -boric acid, 40mmol) is added into a reaction bottle, 300mL of mixed solution of toluene, ethanol and water (the volume ratio of the toluene, the ethanol and the water is the same as that in example 1) is added, nitrogen is used for protection, and the temperature is raised to 90 ℃ for reaction for 24 hours. Cooling and separating out whiteThe colored powder was filtered with suction to give a white solid, which was dissolved in dichloromethane and filtered through a silica gel funnel to give the compound 60(28.90g, yield: 88%, HPLC purity > 99.9%).
The compound 60 thus obtained was subjected to assay, and the results were as follows:
testing by mass spectrometry: a theoretical value of 656.85; the test value was 656.73.
Elemental analysis:
the theoretical values are: c, 85.94; h, 4.91; n, 4.26; s, 4.88;
the test values are: c, 85.93; h, 4.92; n, 4.26; and S, 4.89.
Example 9: synthesis of Compound 74
The synthetic route is as follows:
Figure BDA0002946895790000251
the synthesis process is as follows:
s1, synthesis of intermediate C-74:
after the addition of reactant A-74(55mmol) and reactant B-74(50mmol) to the reaction vessel, Pd (PPh) was added3)4(0.5mmol), potassium carbonate (100mmol), and 300mL of a mixture of solvents toluene, ethanol and water (volume ratio of toluene, ethanol and water as in example 1), and the air was sufficiently replaced with nitrogen three times; the temperature was raised to 90 ℃ and the reaction was carried out for about 18 hours. And after the reaction is finished, cooling, separating liquid, spin-drying the organic solvent to obtain a white solid, dissolving the white solid by using dichloromethane about 30mL, and then passing through a silica gel column, wherein dichloromethane: petroleum ether is 1: 3 most of the product was flushed out and after spin-drying, a white intermediate C-74(46mmol) was obtained.
S2, synthesis of compound 74:
pd (PPh)3)4(0.4mmol), potassium carbonate (80mmol), intermediate C-74(45mmol) and reactant D-74(40mmol) were added to a reaction flask, and 300mL of a mixture of toluene, ethanol and water (volume ratio of toluene, ethanol and water as in example 1) were added thereto, and the mixture was heated to 90 ℃ under nitrogen protection for 24 hours. Cooling, separating out white powder, vacuum filtering to obtain white solid, dissolving in dichloromethaneAfter silica gel funnel, the indicated compound 74 was obtained (24.02g, yield: 91%, HPLC purity > 99.9%).
The compound 60 thus obtained was subjected to assay, and the results were as follows:
testing by mass spectrometry: a theoretical value of 659.81; the test value was 659.74.
Elemental analysis:
the theoretical values are: c, 80.10; h, 4.43; n, 10.61; s, 4.86;
the test values are: c, 80.09; h, 4.44; n, 10.63; and S, 4.86.
Example 10: synthesis of Compound 83
The synthetic route is as follows:
Figure BDA0002946895790000261
the synthesis process is as follows:
pd (pph)3)4(0.5mmol), potassium carbonate (100mmol), reactant A-83(110mmol) and reactant B-83(50mmol) were charged into a reaction flask, and 300mL of a mixture of toluene, ethanol and water (volume ratio of toluene, ethanol and water as in example 1) were added thereto, and the mixture was heated to 90 ℃ under nitrogen protection for 24 hours. After cooling, a white powder was precipitated, which was filtered to obtain a white solid, which was dissolved in methylene chloride and passed through a silica gel funnel to obtain the compound 83(27.82g, yield: 92%, HPLC purity > 99.9%).
The detection analysis of the obtained compound 83 was carried out, and the results were as follows:
testing by mass spectrometry: a theoretical value of 676.86; the test value was 676.51.
Elemental analysis:
the theoretical values are: c, 92.28; h, 5.36; o, 2.36;
the test values are: c, 92.26; h, 5.37; o, 2.35.
Example 11: synthesis of Compound 99
The synthetic route is as follows:
Figure BDA0002946895790000271
the synthesis process is as follows:
pd (pph)3)4(0.5mmol), potassium carbonate (100mmol), reactant A-99(110mmol) and reactant B-99(50mmol) were charged into a reaction flask, and 300mL of a mixture of toluene, ethanol and water (volume ratio of toluene, ethanol and water as in example 1) was added thereto, and the mixture was heated to 90 ℃ under nitrogen protection for 24 hours. After cooling, a white powder was precipitated, which was filtered to obtain a white solid, which was dissolved in methylene chloride and passed through a silica gel funnel to obtain the indicated compound 99(28.69g, yield: 89%, HPLC purity > 99.9%).
The detection analysis of the obtained compound 83 was carried out, and the results were as follows:
testing by mass spectrometry: a theoretical value of 644.80; the test value was 644.67.
Elemental analysis:
the theoretical values are: c, 81.96; h, 4.38; n, 8.69; s, 4.97;
the test values are: c, 81.97; h, 4.39; n, 8.68; s, 4.97.
Organic light emitting device example 1
The organic electroluminescent device includes: the structure comprises a substrate, an ITO anode, a hole injection layer, a hole transport layer, a light-emitting layer, a first electron transport layer, a second electron transport layer, a cathode (a magnesium-silver electrode, the mass ratio of magnesium to silver is 9:1) and a cap layer (CPL), wherein the thickness of the ITO anode is 15nm, the thickness of the hole injection layer is 5nm, the thickness of the hole transport layer is 70nm, the thickness of the light-emitting layer is 25nm, the thickness of the first electron transport layer is 30nm, the thickness of the second electron transport layer is 5nm, the thickness of the magnesium-silver electrode is 14nm and the thickness of the cap layer (CPL) is 100 nm.
Preparation of organic electroluminescent device:
the glass substrate was cleaned by sonicating in isopropanol and deionized water for 30 minutes, respectively, and then exposing to ozone for about 10 minutes; mounting the obtained glass substrate with the ITO anode on a vacuum deposition device; evaporating a hole injection layer material HAT-CN on the ITO anode layer in a vacuum evaporation mode, wherein the thickness of the hole injection layer material HAT-CN is 5nm, and the hole injection layer is used as a hole injection layer; in thatThe material of a hole transport layer which is vacuum evaporated on the hole injection layer is TAPC, the thickness of the hole transport layer is 70nm, and the hole transport layer is used as the hole transport layer; co-depositing a light-emitting layer on the hole transport layer, wherein CBP is used as a host material, Ir (ppy)3As doping material, Ir (ppy)3The mass ratio of CBP to CBP is 0.5: 9.5, and the thickness is 25 nm; vacuum evaporating a first electron transport layer on the light-emitting layer, wherein the material of the first electron transport layer is TPBI, and the thickness of the first electron transport layer is 30 nm; vacuum evaporating a second electron transport layer on the first electron transport layer, wherein the second electron transport layer is made of Alq3The thickness is 5 nm; vacuum evaporating a magnesium-silver electrode on the second electron transport layer, wherein the mass ratio of Mg to Ag is 9:1, the thickness is 14nm, and the magnesium-silver electrode is used as a cathode; compound 1 of the present invention was vacuum-deposited on a cathode to a thickness of 100nm and used as a cathode cap layer (CPL).
Organic light emitting device embodiments 2 to 11
Organic light-emitting devices 2 to 11 were prepared by following the procedure of organic light-emitting device example 1, except that the cathode cap layer material compound 1 was replaced with compounds 23, 25, 29, 40, 49, 58, 60, 74, 83 and 99, respectively, and the other layers were the same.
Comparative example 1 of organic light emitting device
An organic light emitting device was prepared according to the procedure of example 1 except that the cathode cap layer material compound 1 was replaced with CBP and the other layers were the same.
Example 12
The five-membered heterocyclic compounds obtained in examples 1 to 11 and the comparative compound Alq were each added3The thermal properties and refractive indices were tested and the results are shown in table 1.
TABLE 1 five-membered heterocyclic compounds obtained in examples 1 to 11 and comparative compound Alq3Performance of
Figure BDA0002946895790000281
Figure BDA0002946895790000291
Note: the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the refractive index n is measured by an ellipsometer (U.S. J.A. Woollam Co. model: ALPHA-SE) under an atmospheric environment.
As can be seen from Table 1, for visible light with a wavelength of 450-635nm, the refractive indexes of the five-membered heterocyclic compounds of the invention are all greater than 2.0, which meets the refractive index requirement of the light-emitting device on CPL, and therefore, higher light-emitting efficiency can be brought. In addition, the glass transition temperature of the five-membered heterocyclic compounds of the present invention is higher than 150 ℃, thus showing that the heterocyclic compounds have high stability in a thin film state when applied to a light emitting device.
The light emitting properties of the example devices 1 to 11 and the comparative device 1 were tested, and the results are shown in table 2.
TABLE 2 luminescence properties (luminance 5000 cd/m) of the devices2)
Figure BDA0002946895790000292
As can be seen from Table 2 above, the driving voltages of the devices using the five-membered heterocyclic compound of the present invention as the cathode cap layer material were all lower than those of the comparative device 1. Compared with the comparative device 1, the current efficiency and the service life of the device adopting the five-membered heterocyclic compound as the cathode cap layer material are both obviously improved. Therefore, the five-membered heterocyclic compound can improve the luminous efficiency of the luminescent device and prolong the service life of the device, and is an ideal cathode cap layer material.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. 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 (10)

1. A five-membered heterocyclic compound having the structure shown in formula i:
Figure FDA0002946895780000011
wherein:
x is selected from: -O-, -S-, -C (R)15)(R16) -or-N (R)17)-；
X1、X2Independently selected from: c or N;
R1、R2independently selected from: C1-C20 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 5-to 30-membered heteroaryl;
R15、R16、R17independently selected from: C1-C10 alkyl, C1-C10 alkoxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted 5-60 membered heteroaryl; or R15And R16Bonding to form a ring;
L1、L2independently selected from: single bond, C1-C10 alkyl, halogen, protium, deuterium, tritium, C1-C10 alkyl substituted or unsubstituted phenyl, naphthyl, biphenyl, terphenyl, anthracenyl, pyridyl;
Ar1、Ar2independently selected from the structures shown in formulas II-IV:
Figure FDA0002946895780000012
in formula II:
R3、R4、R5、R6independently selected from: a connecting bond, a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a substituted or unsubstituted C1-C6 chain alkyl group, a substituted or unsubstituted C5-C10 cycloalkyl group, a substituted or unsubstituted C2-C6 chain alkenyl group, a substituted or unsubstituted C1-C6 chain alkoxy groupSubstituted or unsubstituted C5-C10 cycloalkoxy, substituted or unsubstituted aromatic hydrocarbon group, C1-C10 alkyl-substituted or unsubstituted aromatic heterocyclic group, substituted or unsubstituted condensed polycyclic aromatic group, substituted or unsubstituted aryloxy group;
Y1、Y2、Y3independently selected from: a carbon atom, an oxygen atom, a sulfur atom or a nitrogen atom; wherein the number of oxygen atoms is not more than 1, and the number of sulfur atoms is not more than 1;
Ar3、Ar4、Ar5independently selected from: a connecting bond, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic group;
wherein R is3、R4、R5、R6、Ar3、Ar4And Ar51 of them is a connecting bond;
in formula III:
R7、R8、R9independently selected from: a connecting bond, C1-C10 chain alkyl, halogen, protium, deuterium, tritium, C1-C10 alkyl substituted or unsubstituted phenyl, naphthyl, biphenylyl, terphenyl, anthracenyl, pyridyl, dibenzofuranyl, dibenzothiazolyl, 9-dimethylfluorene, N-phenylcarbazole; and R is7、R8And R91 of them is a connecting bond;
Z1、Z2、Z3independently selected from: a carbon atom or a nitrogen atom;
in formula IV:
R10、R11、R12、R13、R14independently selected from: a connecting bond, a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a substituted or unsubstituted C1-C6 chain alkyl group, a substituted or unsubstituted C5-C10 cycloalkyl group, a substituted or unsubstituted C2-C6 chain alkenyl group, a substituted or unsubstituted C1-C6 chain alkoxy group, a substituted or unsubstituted C5-C10 cycloalkoxy group, a substituted or unsubstituted aromatic hydrocarbon group, a C1-C10 alkyl-substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted condensed polycyclic aromatic hydrocarbonA group, substituted or unsubstituted aryloxy; and R is10、R11、R12、R13And R141 of them is a connecting bond;
A1、A2、A3、A4independently selected from: carbon atoms or nitrogen atoms.
2. The five-membered heterocyclic compound according to claim 1,
the R is1、R2The method comprises the following steps:
in the substituted or unsubstituted C6-C30 aryl and the substituted or unsubstituted 5-to 30-membered heteroaryl, the substituent is selected from: protium, deuterium, tritium, halogen, cyano, C1-C20 alkyl, C1-C20 alkoxy, C6-C20 aryl, 5-20 membered heteroaryl;
in the substituted or unsubstituted 5-30-membered heteroaryl, the heteroatom of the heteroaryl is selected from the group consisting of: nitrogen, oxygen or sulfur;
the R is15、R16、R17The method comprises the following steps:
in the substituted or unsubstituted C6-C60 aryl and the substituted or unsubstituted 5-60-membered heteroaryl, the substituent is selected from the following groups: protium, deuterium, tritium, halogen, cyano, C1-C20 alkyl, C1-C20 alkoxy, C6-C20 aryl, 5-20 membered heteroaryl;
in the substituted or unsubstituted 5-60-membered heteroaryl, the heteroatom of the heteroaryl is selected from the group consisting of: nitrogen, oxygen or sulfur;
the R is3、R4、R5、R6The method comprises the following steps:
in the formula III, Z1、Z2、Z3When all are nitrogen atoms, in the formula I, Ar1、Ar2At most 1 of them is the structure shown in formula III.
3. The five-membered heterocyclyl compound according to claim 1, selected from the following structures:
Figure FDA0002946895780000031
Figure FDA0002946895780000041
Figure FDA0002946895780000051
Figure FDA0002946895780000061
4. a method for producing a five-membered heterocyclic group compound according to any one of claims 1 to 3, characterized by comprising the steps of:
reacting the reactant A, the reactant B and the reactant C to obtain a compound shown as a formula I;
Figure FDA0002946895780000071
5. the method according to claim 4, wherein the reaction temperature is 80 to 120 ℃.
6. The method according to claim 4, wherein Ar is Ar1≠Ar2And/or L1≠L2The preparation method comprises the following steps:
a) reacting reactant A with reactant B to form intermediate D;
b) reacting the intermediate D with a reactant C to form a compound shown as a formula I;
Figure FDA0002946895780000072
or
Ar1＝Ar2And L is1＝L2The preparation method comprises the following steps: reacting the reactant A with the reactant B to form the compound shown in the formula I.
7. An organic electroluminescent element, characterized in that at least one functional layer of the organic electroluminescent element contains the five-membered heterocyclic compound according to any one of claims 1 to 3.
8. The organic electroluminescent device according to claim 7, wherein the CPL layer of the organic electroluminescent device contains the five-membered heterocyclic compound according to any one of claims 1 to 3.
9. The organic electroluminescent device according to claim 7 or 8, wherein the hole blocking layer and/or the electron transport layer of the organic electroluminescent device contains the five-membered heterocyclic compound according to any one of claims 1 to 3.
10. An element, characterized in that the element is a lighting or display element; the element comprising the organic electroluminescent device according to any one of claims 7 to 9.
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