CN110105225B - Organic electroluminescent material and organic electroluminescent device containing same - Google Patents

Organic electroluminescent material and organic electroluminescent device containing same Download PDF

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CN110105225B
CN110105225B CN201910401738.1A CN201910401738A CN110105225B CN 110105225 B CN110105225 B CN 110105225B CN 201910401738 A CN201910401738 A CN 201910401738A CN 110105225 B CN110105225 B CN 110105225B
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organic electroluminescent
transport layer
substituted
hole transport
unsubstituted
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CN110105225A (en
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马天天
冯震
李红燕
李健
沙荀姗
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Shaanxi Lighte Optoelectronics Material Co Ltd
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Abstract

An organic electroluminescent material and an organic electroluminescent device containing the material are disclosed, wherein a novel aryl group-dihydrophenanthrene is introduced as one of core groups to obtain a dihydrophenanthrene derivative, and the dihydrophenanthrene derivative has a larger molecular weight and can increase the glass transition temperature and the decomposition temperature of the material, so that the thermal stability of the material is enhanced, and the service life of the device is prolonged; the compound containing the dihydrophenanthrene group has excellent hole transport performance, can be used for manufacturing an organic electroluminescent device, can be used as a hole injection layer, a hole transport layer and the like in the organic electroluminescent device, and is particularly used as a hole transport layer material in the organic electroluminescent device to improve the recombination of electrons and holes in the OLED device, so that the driving voltage can be effectively reduced, the luminous efficiency of the organic electroluminescent device is improved, and the service life of the organic electroluminescent device is prolonged.

Description

Organic electroluminescent material and organic electroluminescent device containing same
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to an organic electroluminescent material and an organic electroluminescent device containing the same.
Background
In recent years, Organic electroluminescent devices (OLEDs) have been gradually introduced into the human field of vision as a new generation of display technology. A common organic electroluminescent device is composed of an anode, a cathode, and one or more organic layers disposed between the cathode and the anode. When voltage is applied to the anode and the cathode, the two electrodes generate an electric field, electrons on the cathode side move to the light emitting layer under the action of the electric field, electrons on the anode side also move to the light emitting layer, the electrons and the light emitting layer are combined to form excitons in the light emitting layer, the excitons are in an excited state and release energy outwards, and the process of releasing energy from the excited state to a ground state releases energy emits light outwards. Therefore, it is important to improve the recombination of electrons and holes in the OLED device.
In order to improve the luminance, efficiency and lifetime of organic electroluminescent devices, a multilayer structure is generally used in the devices. These multilayer structures include: a hole injection layer (hole injection layer), a hole transport layer (hole transport layer), an electron-blocking layer (electron-blocking layer), a light-emitting layer (emitting layer), and an electron transport layer (electron transport layer), and the like. These organic layers have the ability to increase the efficiency of carrier (hole and electron) injection between the interfaces of the layers, balancing carrier transport between the layers, and thus increasing the brightness and efficiency of the device.
At present, although a large number of organic electroluminescent materials with excellent properties have been developed successively, for example: CN201380045022.3 provides an aromatic derivative having 9' 9 diphenylfluorene as a skeleton, which is used as an organic electroluminescent material. However, the five-membered ring of fluorene in 9' 9 diphenylfluorene has a large tension, and the bond breaking easily occurs at a high temperature or in an electrically excited state, thereby reducing the performance of the organic electroluminescent device. Therefore, how to design new materials with better performance for adjustment so that all devices can achieve the effects of reducing voltage, improving efficiency and prolonging life is a problem to be solved by those skilled in the art.
The organic electroluminescent device affects efficiency, driving voltage and lifetime, which are the most important, and how to improve the stability of the device is also a very important issue.
Disclosure of Invention
The invention aims to provide an organic electroluminescent material containing dihydrophenanthrene and having excellent performance.
Another object of the present invention is to provide an organic electroluminescent device comprising the organic electroluminescent material, which has a lower driving voltage, higher luminous efficiency and a longer service life.
In order to achieve the purpose, the invention adopts the following technical scheme:
an organic electroluminescent material, the structural formula of which is shown in chemical formula 1;
Figure BDA0002059968730000011
wherein L is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 40 carbon atoms, and a substituted or unsubstituted heteroarylene group having 1 to 40 carbon atoms;
Ar1、Ar2the same or different, each is independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 35 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 35 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 35 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 35 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 35 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 40 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 2 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and a substituted or unsubstituted heteroaryl group having 1 to 40 carbon atoms;
R1、R2、R3、R4the same or different, each is independently selected from hydrogen, deuterium, tritium, substituted or unsubstituted alkyl group having 1 to 35 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 35 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 35 carbon atoms, substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and substituted or unsubstituted heteroaryl group having 1 to 40 carbon atoms;
R5selected from empty, hydrogen or a single bond;
the R is1、R2、R3、R4、Ar1、Ar2And the substituents of L are the same or different and are each independently selected from deuterium, cyano, nitro, halogen, hydroxyl, substituted or unsubstituted alkyl of 1 to 40 carbon atoms, substituted or unsubstituted cycloalkyl of 3 to 40 carbon atoms, substituted or unsubstituted alkenyl of 2 to 40 carbon atoms, substituted or unsubstituted alkynyl of 2 to 40 carbon atoms, substituted or unsubstituted heterocycloalkyl of 2 to 40 carbon atoms, substituted or unsubstituted aralkyl of 7 to 40 carbon atoms, substituted or unsubstituted heteroaralkyl of 2 to 40 carbon atoms, substituted or unsubstituted aryl of 6 to 40 carbon atoms, substituted or unsubstituted heteroaryl of 1 to 40 carbon atoms, substituted or unsubstituted alkoxy of 1 to 40 carbon atoms, substituted or unsubstituted alkylamino of 2 to 40 carbon atoms, substituted or unsubstituted cycloalkyl of 2 to 40 carbon atoms, cycloalkyl, A substituted or unsubstituted arylamino group having 6 to 40 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 40 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 40 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 45 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms.
In a further improvement of the present invention, the structural formula of the organic electroluminescent material is shown in chemical formula 2 or chemical formula 3;
Figure BDA0002059968730000021
Figure BDA0002059968730000031
in a further development of the invention, the R is1、R2、R3、R4The same or different, each is independently selected from hydrogen, substituted or unsubstituted methyl, substituted or unsubstituted phenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted biphenyl, and substituted or unsubstituted naphthaleneAnd (4) a base.
In a further improvement of the present invention, L is selected from the group consisting of a single bond, a substituted or unsubstituted phenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted biphenyl group, and a substituted or unsubstituted naphthyl group.
In a further improvement of the present invention, the structure of chemical formula 1 is specifically as follows:
Figure BDA0002059968730000032
Figure BDA0002059968730000041
Figure BDA0002059968730000051
Figure BDA0002059968730000061
Figure BDA0002059968730000071
an organic electroluminescent device based on the organic electroluminescent material comprises an anode, wherein a hole injection layer is arranged on the anode;
a hole transport layer is arranged on the hole injection layer;
a luminescent layer is arranged on the hole transport layer;
an electron transport layer is arranged on the luminous layer;
an electron injection layer is arranged on the electron transport layer;
a cathode is arranged on the electron injection layer;
wherein the hole transport layer comprises an organic electroluminescent material.
In a further development of the invention, the hole transport layer comprises:
a first hole transport layer and a second hole transport layer;
wherein the first hole transport layer is disposed on the hole injection layer;
the second hole transport layer is disposed on the first hole transport layer;
the light emitting layer is disposed on the second hole transport layer.
In a further development of the invention, the first hole transport layer or the second hole transport layer contains the organic electroluminescent material.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention introduces a novel aryl group-dihydrophenanthrene as one of core groups, the dihydrophenanthrene has a non-conjugated six-membered ring central structure, and the dihedral angle/coplanarity of a triarylamine branched-chain benzene ring can be finely adjusted, so that the balance of better molecular orbital energy level and hole mobility is achieved;
2. the dihydrophenanthrene group has a plurality of substitutable sites, so that better expansibility is achieved; by optimizing the combination of the selected substituent groups, the intermolecular stacking mode can be optimized, and the performance of a material device is improved;
3. according to the invention, a novel aryl group-dihydrophenanthrene is introduced as one of core groups to obtain a dihydrophenanthrene derivative, and the dihydrophenanthrene derivative has a larger molecular weight and can raise the glass transition temperature and the decomposition temperature of a material, so that the thermal stability of the material is enhanced and the service life of a device is prolonged;
4. the compound containing dihydrophenanthrene group has excellent hole transport performance, can be used for manufacturing organic electroluminescent devices, can be used as a hole injection layer, a hole transport layer and the like in the organic electroluminescent devices, and is particularly used as a hole transport layer material in the organic electroluminescent devices, so that the recombination of electrons and holes in the OLED devices is improved, the driving voltage can be effectively reduced, the luminous efficiency of the organic electroluminescent devices is improved, and the service life of the organic electroluminescent devices is prolonged.
Drawings
Fig. 1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention;
fig. 2 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.
In the figure, 1 is an anode, 2 is a hole injection layer, 3 is a hole transport layer, 4 is a light emitting layer, 5 is an electron transport layer, 6 is an electron injection layer, 7 is a cathode, 8 is a capping layer, 9 is a first hole transport layer, and 10 is a second hole transport layer.
Detailed Description
The present invention will be described in further detail below with reference to examples. However, the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Hereinafter, an organic electroluminescent device according to an embodiment will be explained. Explanations will be mainly given regarding features other than the compound according to one embodiment, and unexplained portions will be in accordance with the above description.
The structural formula of the organic electroluminescent material provided by the invention is shown in chemical formula 1;
Figure BDA0002059968730000081
wherein L is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 40 carbon atoms, and a substituted or unsubstituted heteroarylene group having 1 to 40 carbon atoms;
Ar1、Ar2the same or different, each is independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 35 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 35 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 35 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 35 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 35 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 40 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 2 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and a substituted or unsubstituted heteroaryl group having 1 to 40 carbon atoms;
R1、R2、R3、R4the same or different, are respectively and independently selected from hydrogen, deuterium, tritium, substituted or unsubstituted C1-35An alkyl group, a substituted or unsubstituted alkenyl group having 2 to 35 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 35 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 1 to 40 carbon atoms;
R5selected from empty, hydrogen or a single bond;
the R is1、R2、R3、R4、Ar1、Ar2And the substituents of L are the same or different and are each independently selected from deuterium, cyano, nitro, halogen, hydroxyl, substituted or unsubstituted alkyl of 1 to 40 carbon atoms, substituted or unsubstituted cycloalkyl of 3 to 40 carbon atoms, substituted or unsubstituted alkenyl of 2 to 40 carbon atoms, substituted or unsubstituted alkynyl of 2 to 40 carbon atoms, substituted or unsubstituted heterocycloalkyl of 2 to 40 carbon atoms, substituted or unsubstituted aralkyl of 7 to 40 carbon atoms, substituted or unsubstituted heteroaralkyl of 2 to 40 carbon atoms, substituted or unsubstituted aryl of 6 to 40 carbon atoms, substituted or unsubstituted heteroaryl of 1 to 40 carbon atoms, substituted or unsubstituted alkoxy of 1 to 40 carbon atoms, substituted or unsubstituted alkylamino of 2 to 40 carbon atoms, substituted or unsubstituted cycloalkyl of 2 to 40 carbon atoms, cycloalkyl, A substituted or unsubstituted arylamino group having 6 to 40 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 40 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 40 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 45 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms.
Preferably, the structural formula of the organic electroluminescent material is shown in chemical formula 2 or chemical formula 3;
Figure BDA0002059968730000091
preferably, said R is1、R2、R3、R4Same or different, each independently selected from hydrogen, substituted or unsubstituted methyl, substituted or unsubstitutedSubstituted phenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted biphenyl, and substituted or unsubstituted naphthyl.
Preferably, L is selected from the group consisting of a single bond, a substituted or unsubstituted phenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted biphenyl group, and a substituted or unsubstituted naphthyl group.
Preferably, the structure of chemical formula 1 is specifically as follows, but not limited thereto:
Figure BDA0002059968730000101
Figure BDA0002059968730000111
Figure BDA0002059968730000121
Figure BDA0002059968730000131
Figure BDA0002059968730000141
an organic electroluminescent device of the material comprises an anode, wherein a hole injection layer is arranged on the anode;
a hole transport layer is arranged on the hole injection layer;
a luminescent layer is arranged on the hole transport layer;
an electron transport layer is arranged on the luminous layer;
an electron injection layer is arranged on the electron transport layer;
a cathode is arranged on the electron injection layer;
wherein the hole transport layer comprises an organic electroluminescent material.
Preferably, the hole transport layer includes:
a first hole transport layer and a second hole transport layer;
wherein the first hole transport layer is disposed on the hole injection layer;
the second hole transport layer is disposed on the first hole transport layer;
the light emitting layer is disposed on the second hole transport layer.
Preferably, the first hole transport layer or the second hole transport layer includes the organic electroluminescent material.
Fig. 1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention; fig. 2 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.
As shown in fig. 1, the organic electroluminescent device according to one embodiment includes an anode 1, a Hole Injection Layer (HIL)2, a Hole Transport Layer (HTL)3, an emission layer (EML)4, an Electron Transport Layer (ETL)5, an Electron Injection Layer (EIL)6, a cathode 7, and a capping layer (CPL) 8.
In general, the anode 1 is made of transparent metal oxide, such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), zinc oxide (ZnO), or Indium Tin Zinc Oxide (ITZO).
A hole injection layer 2 is disposed on the anode 1, and a hole transport layer 2 is disposed on the hole injection layer 3, wherein the hole transport layer 3 includes an organic electroluminescent material represented by chemical formula 1.
As shown in fig. 2, the hole transport layer 3 may include a first hole transport layer (HT1)9 and a second hole transport layer (HT2) 10. Among the plurality of hole transport layers, a second hole transport layer (HT2)10 is adjacent to the light emitting layer (EML)4, and specifically, a first hole transport layer 9 is disposed on the hole transport layer 2, a second hole transport layer 10 is disposed on the first hole transport layer 9, and the light emitting layer 4 is disposed on the second hole transport layer 10. Wherein the first hole transport layer and the second hole transport layer each include an organic electroluminescent material represented by chemical formula 1.
The unsubstituted alkyl group in the present invention means a linear alkyl group having 1 to 35 carbon atoms or a branched alkyl group having 1 to 13 carbon atoms. For example, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, hexyl and the like. The substituted alkyl group having 1 to 35 carbon atoms means that at least one hydrogen atom is substituted with deuterium atom, F, Cl, I, CN, hydroxyl group, nitro group, amino group, or the like.
The unsubstituted alkenyl group in the present invention refers to an alkenyl group having 2 to 35 carbon atoms, a straight-chain alkenyl group having 2 to 40 carbon atoms including a carbon-carbon double bond, or a branched-chain alkenyl group having 1 to 13 carbon atoms. For example: vinyl, propenyl, allyl, isopropenyl, 2-butenyl, and the like. The substituted alkenyl group having 2 to 35 carbon atoms means that at least one hydrogen atom is substituted with deuterium atom, F, Cl, I, CN, hydroxyl group, nitro group, amino group or the like.
The unsubstituted alkynyl group in the present invention refers to an alkynyl group having 2 to 35 carbon atoms, a straight-chain alkynyl group having 2 to 35 carbon atoms containing a carbon-carbon triple bond, or a branched-chain alkynyl group having 1 to 10 carbon atoms. For example: ethynyl, 2-propynyl, and the like. The substituted alkynyl group having 2 to 35 carbon atoms means that at least one hydrogen atom is substituted with deuterium atom, F, Cl, I, CN, hydroxyl group, nitro group, amino group or the like.
The unsubstituted aryl group in the present invention means an aryl group having 6 to 40 carbon atoms. For example: phenyl, naphthyl, pyrenyl, dimethylfluorenyl, anthracenyl, phenanthrenyl,
Figure BDA0002059968730000152
Mesityl, azunyl, acenaphthenyl, biphenyl, benzanthryl, spirobifluorenyl, perylenyl, indenyl, and the like. The substituted aryl group having 6 to 40 carbon atoms means that at least one hydrogen atom is substituted with deuterium atom, F, Cl, I, CN, hydroxyl group, nitro group, amino group, or the like.
The unsubstituted aralkyl group in the present invention means an aralkyl group having 7 to 40 carbon atoms. For example: tolyl, dimethylfluorenyl, and the like. The substituted aralkyl group having 7 to 40 carbon atoms means that at least one hydrogen atom is substituted with deuterium atom, F, Cl, I, CN, hydroxyl group, nitro group, amino group, or the like.
The unsubstituted heteroaryl group in the present invention means a heteroaryl group having 2 to 40 carbon atoms. For example: pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, quinolinyl, indolyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, dibenzoselenophenyl, and the like. Substituted heteroaryl having 2 to 40 carbon atoms means that at least one hydrogen atom is substituted with deuterium atom, F, Cl, I, CN, hydroxyl, nitro, amino, or the like.
The unsubstituted cycloalkyl group in the present invention means a cycloalkyl group having 3 to 40 carbon atoms. For example: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl and the like. The substituted cycloalkyl group having 3 to 40 carbon atoms means that at least one hydrogen atom is substituted with deuterium atom, F, Cl, I, CN, hydroxyl group, nitro group, amino group or the like.
The following description will be made by way of specific examples.
Synthesis of Compound 1
Figure BDA0002059968730000151
Adding 2-bromotoluene (10.0g,58.5mmol), 4-chlorobenzeneboronic acid (11.0g,70.2mmol), tetrakistriphenylphosphine palladium (1.35g,1.17mmol), potassium carbonate (16.2g,117mmol), tetrabutylammonium bromide (3.77g,11.7mmol), toluene (60mL), ethanol (60mL) and deionized water (60mL) into a round bottom flask, heating to 75-80 ℃ under nitrogen protection, and stirring for 8 hours; cooling the reaction solution to room temperature, adding toluene (100mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by recrystallization from a dichloromethane/ethanol system to give intermediate I-A-1(9.80g, 83%) as a pale yellow solid.
Figure BDA0002059968730000161
Intermediate I-A-1(9.80g,48.4mmol), N-bromosuccinimide (9.04g,50.8mmol), azobisisobutyronitrile (20mg), and carbon tetrachloride (100mL) were added to a round bottom flask, warmed under nitrogen, and stirred at 77 ℃ for 2 hours; cooling the reaction solution to room temperature, and removing the solvent under reduced pressure; purification by column chromatography on silica gel using dichloromethane/n-heptane (1:5) as mobile phase gave intermediate I-A-2 as a white solid (6.81g, 50%).
Figure BDA0002059968730000162
Magnesium strips (0.71g,29.0mmol) and ether (10mL) were placed in a dry round bottom flask under nitrogen and iodine (10mg) was added. Then, slowly dripping the diethyl ether (20mL) solution dissolved with the intermediate I-A-2(6.81g,24.2mmol) into the flask, heating to 35 ℃ after finishing dripping, and stirring for 1 hour; cooling the reaction solution to 0 ℃, slowly dropping an ether (5mL) solution dissolved with acetone (1.12g,19.3mmol), heating to 35 ℃ after dropping, and stirring for 2 hours; cooling the reaction solution to room temperature, adding 5% hydrochloric acid to the reaction solution until the pH value is less than 7, stirring the solution for 1 hour, adding diethyl ether (50mL) to the solution for extraction, combining organic phases, drying the organic phases by using anhydrous magnesium sulfate, filtering the mixture, and removing the solvent under reduced pressure; the crude product was purified by silica gel column chromatography using ethyl acetate/n-heptane (1:5) as the mobile phase to give intermediate I-A-3(4.55g, 72%) as a white solid.
Figure BDA0002059968730000163
Adding intermediate I-A-3(4.55g,17.4mmol), trifluoroacetic acid (3.98g,34.9mmol) and dichloromethane (50mL) into a round-bottom flask, and stirring under nitrogen for 6 hours; then, an aqueous sodium hydroxide solution was added to the reaction solution to adjust the reaction solution to pH 8, followed by liquid separation, and the organic phase was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure; the crude product was purified by silica gel column chromatography using dichloromethane/n-heptane (1:2) to give intermediate I-A (3.80g, 90%) as a white solid.
Figure BDA0002059968730000164
4-bromobiphenyl (10.0g,42.9mmol), 2-amino-9, 9-dimethylfluorene (9.88g,47.2mmol), tris (dibenzylideneacetone) dipalladium (0.39g,0.43mmol), 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (0.41g,0.86mmol) and sodium tert-butoxide (6.18g,64.3mmol) were added to toluene (100mL), heated to 105 ℃ under nitrogen protection and stirred for 1 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/ethanol system to yield intermediate II-A as a pale gray solid (13.1g, 84%).
Figure BDA0002059968730000171
Adding the intermediate I-A (3.80g,15.7mmol), the intermediate II-A (5.66g,15.7mmol), the tris (dibenzylideneacetone) dipalladium (0.29g,0.31mmol), the 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.26g,0.63mmol) and the sodium tert-butoxide (2.26g,23.5mmol) into toluene (30mL), heating to 110 ℃ under the protection of nitrogen, and stirring for 16 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/ethyl acetate system to yield compound 1 as a white solid (5.55g, 62%). Mass spectrum: m/z 568.3(M + H)+
Synthesis of Compound 2
Figure BDA0002059968730000172
Adding 2-bromobiphenyl (15.0g,64.4mmol), 2-amino-9, 9-dimethylfluorene (14.8g,70.8mmol), tris (dibenzylideneacetone) dipalladium (0.59g,0.64mmol), 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (0.61g,1.29mmol) and sodium tert-butoxide (9.28g,96.5mmol) into toluene (150mL), heating to 105 ℃ under nitrogen protection, stirring for 4 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/n-heptane system to yield intermediate II-B as a grey solid (18.7g, 80%).
Figure BDA0002059968730000181
Intermediate I-a (5.00g,20.7mmol), intermediate II-B (7.46g,20.7mmol), tris (dibenzylideneacetone) dipalladium (0.38g,0.41mmol), 2-dicyclohexylphosphonium-2, 6-dimethoxybiphenyl (0.34g,0.83mmol) and sodium tert-butoxide (2.98g,31.0mmol) were added to toluene (40mL), heated to 105 ℃ under nitrogen and stirred for 20 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/ethyl acetate system to yield compound 2 as a white solid (6.82g, 58%). Mass spectrum: m/z 568.3(M + H)+
Synthesis of Compound 3
Figure BDA0002059968730000182
Adding 2-bromo-N-phenylcarbazole (10.0g,31.0mmol), 2-aminobiphenyl (5.78g,34.1mmol), tris (dibenzylideneacetone) dipalladium (0.28g,0.31mmol), 2-dicyclohexyl-phosphorus-2, 4, 6-triisopropyl-biphenyl (0.30g,0.62mmol) and sodium tert-butoxide (4.47g,46.6mmol) into toluene (100mL), heating to 105-; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/n-heptane system to yield intermediate II-C as a white solid (9.88g, 78%).
Figure BDA0002059968730000183
Adding the intermediate I-A (5.00g,20.7mmol), the intermediate II-C (9.32g,20.7mmol), the tris (dibenzylideneacetone) dipalladium (0.38g,0.41mmol), the 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.34g,0.83mmol) and the sodium tert-butoxide (2.98g,31.0mmol) into toluene (40mL), heating to 110 ℃ under the protection of nitrogen, and stirring for 18 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloroethane system to give compound 3 as a white solid (7.90g, 62%). Mass spectrum: m/z 617.3(M + H)+
Synthesis of Compound 4
Figure BDA0002059968730000191
Adding 1-bromo-2-isopropylbenzene (15.0g,75.3mmol), 4-chlorobenzeneboronic acid (14.1g,90.4mmol), tetrakistriphenylphosphine palladium (1.74g,1.51mmol), potassium carbonate (20.8g,151mmol), tetrabutylammonium bromide (4.86 g,15.1mmol), toluene (80mL), ethanol (80mL) and deionized water (80mL) into a round-bottomed flask, heating to 75-80 ℃ under nitrogen protection, and stirring for 16 hours; cooling the reaction solution to room temperature, adding toluene (150mL) for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, filtering, and removing the solvent under reduced pressure; the crude product was purified by recrystallization from dichloromethane/n-heptane to yield intermediate I-B-1 as a yellow solid (7.89g, 45%).
Figure BDA0002059968730000192
Adding intermediate I-B-1(7.89g,34.2mmol), N-bromosuccinimide (6.69g,37.6mmol), azobisisobutyronitrile (20mg) and carbon tetrachloride (100mL) to a round-bottom flask, heating under nitrogen, and stirring at 77 ℃ for 1 hour; cooling the reaction solution to room temperature, and removing the solvent under reduced pressure; purification by column chromatography on silica gel using dichloromethane/n-heptane (1:4) as mobile phase gave intermediate I-B-2 as a white solid (6.57g, 62%).
Figure BDA0002059968730000193
Magnesium strips (0.61g,25.5mmol) and ether (10mL) were placed in a dry round bottom flask under nitrogen and iodine (10mg) was added. Then, slowly dripping the diethyl ether (15mL) solution dissolved with the intermediate I-B-2(6.57g,21.2mmol) into the flask, heating to 35 ℃ after finishing dripping, and stirring for 1.5 hours; cooling the reaction solution to 0 ℃, slowly dropping an ether (5mL) solution dissolved with acetone (0.99g,17.0mmol), heating to 35 ℃ after dropping, and stirring for 6 hours; cooling the reaction solution to room temperature, adding 5% hydrochloric acid to the reaction solution until the pH of the reaction solution is less than 7, stirring the reaction solution for 1 hour, adding diethyl ether (50mL) to the reaction solution for extraction, combining organic phases, drying the organic phases by using anhydrous magnesium sulfate, filtering the mixture, and removing the solvent under reduced pressure; the crude product was purified by silica gel column chromatography using ethyl acetate/n-heptane (1:3) as the mobile phase to give intermediate I-B-3(4.10g, 67%) as a white solid.
Figure BDA0002059968730000201
Adding intermediate I-B-3(4.10g,14.2mmol), trifluoroacetic acid (3.23g,28.4mmol) and dichloromethane (40mL) into a round-bottom flask, and stirring under nitrogen for 8 hours; then, an aqueous sodium hydroxide solution was added to the reaction solution to adjust the reaction solution to pH 8, followed by liquid separation, and the organic phase was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure; the crude product was purified by silica gel column chromatography using dichloromethane/n-heptane (1:2) to give intermediate I-B as a white solid (3.66g, 95%).
Figure BDA0002059968730000202
Adding 2-bromo-N-phenylcarbazole (5.00g,15.5mmol), 4-aminobiphenyl (2.89g,17.1mmol), tris (dibenzylideneacetone) dipalladium (0.14g,0.16mmol), 2-dicyclohexyl-phosphorus-2, 4, 6-triisopropyl-biphenyl (0.15g,0.31mmol) and sodium tert-butoxide (2.24g,23.3mmol) into toluene (50mL), heating to 105 ℃ under nitrogen protection, and stirring for 1 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/n-heptane system to yield intermediate II-D as a pale gray solid (5.44g, 85%).
Figure BDA0002059968730000203
Intermediate I-B (3.50g,12.9mmol), intermediate II-D (5.31g,12.9mmol), tris (dibenzylideneacetone) dipalladium (0.24g,0.26mmol)mmol), 2-dicyclohexyl phosphorus-2, 6-dimethoxy biphenyl (0.21g,0.52mmol) and sodium tert-butoxide (1.86g,19.4mmol) were added into toluene (30mL), heated to 105 ℃ under nitrogen protection and stirred for 12 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a toluene/n-heptane system to yield compound 4 as a white solid (4.04g, 48%). Mass spectrum: 645.3(M + H)+
Synthesis of Compound 5
Figure BDA0002059968730000211
Magnesium strips (1.11g,46.2mmol) and ether (10mL) were placed in a dry round bottom flask under nitrogen and iodine (10mg) was added. Then, slowly dripping the diethyl ether (20mL) solution dissolved with the intermediate I-A-2(10.0g,35.5mmol) into the flask, heating to 35 ℃ after finishing dripping, and stirring for 2 hours; cooling the reaction solution to 0 ℃, slowly dropping an ether (10mL) solution in which benzophenone (4.53g,24.9mmol) is dissolved, heating to 35 ℃ after dropping, and stirring for 8 hours; cooling the reaction solution to room temperature, adding 5% hydrochloric acid to the reaction solution until the pH value is less than 7, stirring the solution for 1 hour, adding ether (100mL) to the solution for extraction, combining organic phases, drying the organic phases by using anhydrous magnesium sulfate, filtering the mixture, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using ethyl acetate/n-heptane (1:4) as the mobile phase to give intermediate I-C-3(7.52g, 55%) as a white solid.
Figure BDA0002059968730000212
Intermediate I-C-3(7.52g,19.5mmol), trifluoroacetic acid (4.45g,39.1mmol) and dichloromethane (40mL) were added to a round bottom flask and stirred under nitrogen for 4 hours; then, an aqueous sodium hydroxide solution was added to the reaction solution to adjust the reaction solution to pH 8, followed by liquid separation, and the organic phase was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure; the crude product was purified by silica gel column chromatography using dichloromethane/n-heptane (1:3) to afford intermediates I-C as white solids (6.49g, 91%).
Figure BDA0002059968730000213
Adding the intermediate I-C (3.00g,8.18mmol), the intermediate II-B (2.96g,8.18mmol), tris (dibenzylideneacetone) dipalladium (0.15g,0.16mmol), 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.13g,0.33mmol) and sodium tert-butoxide (1.18g,12.3mmol) into toluene (20mL), heating to 105-; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloroethane/n-heptane system to yield compound 5 as a white solid (3.22g, 61%). Mass spectrum: m/z 692.3(M + H)+
Synthesis of Compound 6
Figure BDA0002059968730000221
2-bromodibenzofuran (10.0g,40.5mmol), 4-aminobiphenyl (7.53g,44.5mmol), tris (dibenzylideneacetone) dipalladium (0.37g,0.40mmol), 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (0.39g,0.81mmol) and sodium tert-butoxide (5.83g,60.7mmol) were added to toluene (100mL), heated to 105-; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using an ethyl acetate/n-heptane system to yield intermediate II-E as a pale gray solid (11.8g, 87%).
Figure BDA0002059968730000222
Intermediate I-C (4.00g,10.9mmol), intermediate II-E (3.66g,10.9mmol), tris (dibenzylideneacetone) dipalladium (0.20g,0.22mmol), 2-dicyclohexylphosphonium-2, 6-dimethoxybiphenyl (0.18g,0.44mmol) and sodium tert-butoxide (1.57g,16.4mmol) were added to toluene (30mL) and heated to 10 deg.F under nitrogenStirring for 12h at 5-110 ℃; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/n-heptane system to yield compound 6 as a white solid (3.98g, 55%). Mass spectrum: 666.3(M + H)+
Synthesis of Compound 7
Figure BDA0002059968730000223
Adding the intermediate I-C (4.50g,12.3mmol), the intermediate II-A (4.43g,12.3mmol), the tris (dibenzylideneacetone) dipalladium (0.22g,0.25mmol), the 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.20g,0.49mmol) and the sodium tert-butoxide (1.77g,18.4mmol) into toluene (30mL), heating to 110 ℃ under the protection of nitrogen, and stirring for 10 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a toluene/n-heptane system to yield compound 7 as a white solid (4.88g, 58%). Mass spectrum: m/z 692.3(M + H)+。
Synthesis of Compound 8
Figure BDA0002059968730000231
Magnesium strips (0.81g,34.1mmol) and ether (10mL) were placed in a dry round bottom flask under nitrogen and iodine (10mg) was added. Then, slowly dripping the diethyl ether (20mL) solution dissolved with the intermediate I-A-2(8.0g,28.4mmol) into the flask, heating to 35 ℃ after finishing dripping, and stirring for 3 hours; cooling the reaction solution to 0 ℃, slowly dropping an ether (20mL) solution in which fluorenone (4.10g,22.7mmol) is dissolved, heating to 35 ℃ after dropping, and stirring for 6 hours; cooling the reaction solution to room temperature, adding 5% hydrochloric acid to the reaction solution until the pH value is less than 7, stirring the solution for 1 hour, adding ether (100mL) to the solution for extraction, combining organic phases, drying the organic phases by using anhydrous magnesium sulfate, filtering the mixture, and removing the solvent under reduced pressure; the crude product was purified by column chromatography on silica gel using ethyl acetate/n-heptane (1:2) as the mobile phase to give intermediate I-D-3(5.40g, 50%) as a white solid.
Figure BDA0002059968730000232
Adding intermediate I-D-3(5.40g,14.1mmol), trifluoroacetic acid (3.22g,39.1mmol) and dichloromethane (30mL) into a round-bottom flask, and stirring under nitrogen for 2 hours; then, an aqueous sodium hydroxide solution was added to the reaction mixture until the pH became 8, followed by liquid separation, drying of the organic phase with anhydrous magnesium sulfate, filtration, and removal of the solvent under reduced pressure; the crude product was purified by silica gel column chromatography using dichloromethane/n-heptane (1:2) to give intermediates I-D as white solids (4.19g, 81%).
Figure BDA0002059968730000233
Adding the intermediate I-D (4.00g,11.0mmol), bis- (4-biphenyl) amine (3.52g,11.0mmol), tris (dibenzylideneacetone) dipalladium (0.20g,0.22mmol), 2-dicyclohexyl phosphorus-2, 6-dimethoxy biphenyl (0.18g,0.44mmol) and sodium tert-butoxide (1.58g,16.4mmol) into toluene (25mL), heating to 105-fold 110 ℃ under the protection of nitrogen, and stirring for 8 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization from toluene to give compound 8 as a white solid (3.35g, 47%). Mass spectrum: m/z 650.3(M + H)+。
Synthesis of Compound 9
Figure BDA0002059968730000241
2-bromodibenzofuran (15.0g,60.7mmol), 2-amino-9, 9-dimethylfluorene (14.0g,66.8mmol), tris (dibenzylideneacetone) dipalladium (0.56g,0.61mmol), 2-dicyclohexyl-phosphorus-2, 4, 6-triisopropylbiphenyl (0.58g,1.21mmol) and sodium tert-butoxide (8.75g,91.1mmol) were added to toluene (120mL), heated to 105 ℃ under nitrogen protection and stirred for 1 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/n-heptane system to yield intermediate II-F as a grey solid (18.2g, 80%).
Figure BDA0002059968730000242
Adding the intermediates I-D (5.00g,13.7mmol), the intermediate 2-F (5.14g,13.7mmol), the tris (dibenzylideneacetone) dipalladium (0.25g,0.27mmol), the 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.23g,0.55mmol) and the sodium tert-butoxide (1.98g,20.6mmol) into toluene (40mL), heating to 110 ℃ under the protection of nitrogen, and stirring for 10 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/n-heptane system to yield compound 9 as a white solid (5.02g, 52%). Mass spectrum: m/z 704.3(M + H)+。
Synthesis of Compound 10
Figure BDA0002059968730000243
2-bromodibenzothiophene (10.0g,38.0mmol), 4-aminobiphenyl (7.07g,41.8mmol), tris (dibenzylideneacetone) dipalladium (0.35g,0.38mmol), 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (0.36g,0.76mmol) and sodium tert-butoxide (5.48g,57.0mmol) were added to toluene (100mL), heated to 105 ℃ under nitrogen protection, and stirred for 1.5 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/ethyl acetate system to yield intermediates II-G (11.5G, 86%) as white solids.
Figure BDA0002059968730000251
Intermediate I-D (4.80G,13.2mmol), intermediate II-G (4.62G,13.2mmol), tris (dibenzylideneacetone) bisAdding palladium (0.24g,0.26mmol), 2-dicyclohexyl phosphorus-2, 6-dimethoxy biphenyl (0.22g,0.53mmol) and sodium tert-butoxide (1.90g,19.7mmol) into toluene (40mL), heating to 105-110 ℃ under the protection of nitrogen, and stirring for 12 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a toluene/n-heptane system to yield compound 10 as a white solid (4.11g, 46%). Mass spectrum: m/z 680.2(M + H)+。
Fabrication of organic electroluminescent device
Example 1: red organic electroluminescent device
The anode was prepared by the following procedure: will have a thickness of
Figure BDA00020599687300002510
The ITO substrate (manufactured by Corning) of (1) was cut into a size of 40mm × 40mm × 0.7.7 mm, prepared into an experimental substrate having a cathode, an anode and an insulating layer pattern using a photolithography process, using ultraviolet ozone and O2:N2The plasma was surface treated to increase the work function of the anode (experimental substrate) and to remove scum.
The m-MTDATA was vacuum-deposited on the test substrate (anode) to a thickness of
Figure BDA0002059968730000252
And NPB is deposited on the hole injection layer to form a thickness of
Figure BDA0002059968730000253
And a first hole transport layer (HT 1).
Vacuum evaporating compound 1 on the first hole transport layer to a thickness of
Figure BDA0002059968730000254
And a second hole transport layer (HT 2).
Evaporating 4,4'-N, N' -dicarbazole-biphenyl (CBP) as main body on the second hole transport layer, and simultaneously doping Ir (acac) with (piq)2Shape ofTo a thickness of
Figure BDA0002059968730000255
The light emitting layer (EML).
DBimiBphen and LiQ are mixed according to the weight ratio of 1:1 and evaporated to form
Figure BDA0002059968730000256
A thick Electron Transport Layer (ETL), and depositing LiQ on the electron transport layer to form a layer with a thickness of
Figure BDA0002059968730000257
And then magnesium (Mg) and silver (Ag) are mixed in a ratio of 1:9 is vacuum-evaporated on the electron injection layer to a thickness of
Figure BDA0002059968730000258
The cathode of (1).
Further, the cathode is deposited with a thickness of
Figure BDA0002059968730000259
N- (4- (9H-carbazol-9-yl) phenyl) -4'- (9H-carbazol-9-yl) -N-phenyl- [1,1' -biphenyl]-4-amine, forming a capping layer (CPL), thereby completing the fabrication of the organic light emitting device.
Organic electroluminescent devices were fabricated by the same method as example 1, except that the compounds shown in table 2 were each used in forming the second hole transport layer (HT 2).
That is, in example 2, the organic electroluminescent device was produced using compound 2, in example 3, the organic electroluminescent device was produced using compound 3, in example 4, the organic electroluminescent device was produced using compound 4, and in example 5, the organic electroluminescent device was produced using compound 5, and the device properties are shown in table 1.
Comparative examples 1 to 2
In the comparative examples 1 to 2, an organic electroluminescent device was fabricated in the same manner as in example 1, except that NPD and TPD were used as the second hole transport layer instead of compound 1.
Comparative example 3
An organic electroluminescent element was produced in the same manner as in example 1 above, except that the second hole transport layer was not formed, and the device properties are shown in table 1.
That is, the organic electroluminescent device was manufactured using NPD in comparative example, and the organic electroluminescent device was manufactured using TPD in comparative example 2, and the device properties are shown in table 1.
For the organic electroluminescent device prepared as above, at 20mA/cm2The device performance was analyzed under the conditions of (1), and the results are shown in table 1 below.
TABLE 1 device Performance of examples 1-5 and comparative examples 1-3
Examples Compound (I) Volt(V) Cd/A EQE T95(h) CIE(x,y)
Example 1 Compound 1 3.58 33.31 22.64 472 (0.677,0.322)
Example 2 Compound 2 3.61 32.80 22.55 510 (0.678,0.321)
Example 3 Compound 3 3.82 33.29 23.95 462 (0.682,0.316)
Example 4 Compound 4 3.98 34.15 20.69 485 (0.680,0.319)
Example 5 Compound 5 3.72 31.12 25.11 468 (0.671,0.328)
Comparative example 1 NPD 5.9 23.15 12.30 280 (0.676,0.323)
Comparative example 2 TPD 6.3 24.22 9.40 310 (0.684,0.314)
Comparative example 3 - 6.1 28.30 9.57 210 (0.683,0.316)
Referring to table 1, it can be seen that in examples 1 to 5, when the compounds 1 to 5 of the present invention were used as second hole transport layer materials for organic electroluminescent devices, the driving voltage (Vlot), current efficiency (Cd/a), and External Quantum Efficiency (EQE) and lifetime (T95) were significantly improved as compared to comparative examples 1 to 3.
As can be seen from examples 1 to 5 and comparative example 3, the organic electroluminescent device using the compound of the present invention as the second hole transport layer (HT2) has a significantly reduced voltage (V), a significantly improved current efficiency (Cd/A) and External Quantum Efficiency (EQE), and an improved lifetime (T95) as compared to the organic electroluminescent device without the second hole transport layer (HT 2).
Examples 1 to 5 showed lower driving voltage and increased efficiency compared to comparative examples 1 to 3.
Specifically, examples 1 and 2 showed superior efficiency, voltage, and life as compared to comparative examples 1 to 3.
Example 6: blue organic electroluminescent device
The anode was prepared by the following procedure: will have a thickness of
Figure BDA0002059968730000261
The ITO substrate (manufactured by Corning) of (1) was cut into a size of 40mm × 40mm × 0.7.7 mm, prepared into an experimental substrate having a cathode, an anode and an insulating layer pattern using a photolithography process, using ultraviolet ozone and O2:N2The plasma was surface treated to increase the work function of the anode (experimental substrate) and to remove scum.
Vacuum evaporation of m-MTDATA on an experimental substrate (anode) to a thickness of
Figure BDA0002059968730000271
And a compound 6 is vacuum-evaporated on the hole injection layer to form a layer having a thickness of
Figure BDA0002059968730000272
And a first hole transport layer (HT 1).
Depositing TCTA on the first hole transport layer to a thickness of
Figure BDA0002059968730000273
And a second hole transport layer (HT 2).
α -AND is taken as a main body, AND 4,4' - (3, 8-diphenylpyrene-1, 6-diylbis (N, N-diphenylaniline) is doped at the same time to form a layer with the thickness of
Figure BDA0002059968730000274
The light emitting layer (EML).
DBimiBphen and LiQ are mixed according to the weight ratio of 1:1 and evaporated to form
Figure BDA0002059968730000275
A thick Electron Transport Layer (ETL), and depositing LiQ on the electron transport layer to form a layer with a thickness of
Figure BDA0002059968730000276
Then magnesium (Mg) and silver (Ag) were mixed at a rate of 1:9, and vacuum-evaporated on the electron injection layer to form an Electron Injection Layer (EIL) having a thickness of
Figure BDA0002059968730000277
The cathode of (1).
Further, the cathode is deposited with a thickness of
Figure BDA0002059968730000278
N- (4- (9H-carbazol-9-yl) phenyl) -4'- (9H-carbazol-9-yl) -N-phenyl- [1,1' -biphenyl]-4-amine, forming a capping layer (CPL), thereby completing the fabrication of the organic light emitting device.
Examples 7 to 10
Organic electroluminescent devices were fabricated by the same method as example 6, except that the compounds shown in table 2 were each used in forming the first hole transport layer (HT 1).
That is, in example 7, the organic electroluminescent element was produced using compound 7, in example 8, the organic electroluminescent element was produced using compound 8, in example 9, the organic electroluminescent element was produced using compound 9, and in example 10, the organic electroluminescent element was produced using compound 10, and the device properties are shown in table 2.
Comparative examples 4 to 6
In comparative examples 4 to 6, organic electroluminescent devices were fabricated in the same manner as in example 6, except that NPB, NPD, TPD were used as the first hole transport layer instead of compound 6.
That is, comparative example 4 produced an organic electroluminescent device using NPB, comparative example 5 produced an organic electroluminescent device using NPD, and comparative example 6 produced an organic electroluminescent device using TPD, and the device properties are shown in table 2.
For the organic electroluminescent device prepared above, at 20mA/cm2The device performance was analyzed under the conditions of (1), and the results are shown in table 2 below.
TABLE 2 device Performance of examples 6-10 and comparative examples 4-6
Examples Compound (I) Volt(V) Cd/A EQE T95(h) CIE(x,y)
Example 6 Compound 6 3.90 7.9 16.3 167 (0.141,0.047)
Example 7 Compound 7 3.88 8.1 16.3 156 (0.142,0.046)
Example 8 Compound 8 4.14 7.2 16.4 173 (0.141,0.047)
Example 9 Compound 9 4.15 7.4 16.5 153 (0.143,0.048)
Example 10 Compound 10 3.95 7.3 15.6 160 (0.142,0.045)
Comparative example 4 NPB 5.20 6.2 10.2 103 (0.140,0.047)
Comparative example 5 NPD 5.00 6.0 10.9 98 (0.141,0.052)
Comparative example 6 TPD 5.5 5.7 6.9 78 (0.140,0.050)
Referring to table 2, in the case of examples 6 to 10 using the compound of the present invention as the first hole transport layer (HT1), the voltage (V), the current efficiency (Cd/a), and the External Quantum Efficiency (EQE) were improved, and the lifetime (T95) exhibited significant improvements, as compared to the compounds of comparative examples 4 to 6.
Therefore, the device manufactured by using the compound of the invention has the characteristics of reducing the driving voltage, improving the luminous efficiency and prolonging the service life.
In conclusion, the compound of the present invention is used as a hole transport layer of an organic electroluminescent device, so that the organic electroluminescent device comprising the compound has lower driving voltage, higher luminous efficiency and better lifetime.
Thermal stability test
The compounds 1 to 10, NPB and NPD were subjected to high-temperature heat treatment, and their glass transition temperatures Tg and decomposition temperatures Td at 1% were measured, and the results are shown in Table 3.
TABLE 3
Compound (I) Tg(℃) Td 1％(℃)
Compound 1 127 368
Compound 2 130 370
Compound 3 128 375
Compound 4 136 405
Compound 5 158 387
Compound 6 145 377
Compound 7 153 390
Compound 8 146 376
Compound 9 129 360
Compound 10 138 400
NPB 100 339
NPD 84 290
As can be seen from the data in Table 3, compounds 1 to 10 of the present invention have higher glass transition temperature and decomposition temperature and better thermal stability than NPB and NPD.
As is apparent from tables 1 to 2 of the organic electroluminescent devices of the examples, when a dihydrophenanthrene group is introduced into an arylamine compound and the compound is used as a hole transport layer material, a high-efficiency and long-life organic electroluminescent device having excellent thermal stability can be manufactured.
The above examples are merely further illustrative of the compounds of the present invention and the scope of the invention as claimed is not limited thereto. It will be apparent to those skilled in the art that various additions and modifications can be made to the present invention without departing from the scope of the technical idea of the present invention as set forth in the claims of the present invention.

Claims (5)

1. An organic electroluminescent material, wherein the structural formula of the material is shown in chemical formula 2 or chemical formula 3;
Figure FDA0002478904730000011
wherein L is a single bond;
Ar1、Ar2the same or different, are respectively and independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted naphthylUnsubstituted biphenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl;
R1、R2the same or different, are respectively and independently selected from methyl and phenyl;
R3、R4the same or different, are respectively and independently selected from hydrogen, methyl and phenyl;
ar is1、Ar2The substituents (A) are the same or different and are each independently selected from a methyl group and an aryl group having 6 carbon atoms.
2. The organic electroluminescent material according to claim 1, wherein the structure of chemical formula 1 is specifically as follows:
Figure FDA0002478904730000012
Figure FDA0002478904730000021
Figure FDA0002478904730000031
3. an organic electroluminescent device based on the organic electroluminescent material according to claim 1 or 2, comprising an anode having a hole injection layer provided thereon;
a hole transport layer is arranged on the hole injection layer;
a luminescent layer is arranged on the hole transport layer;
an electron transport layer is arranged on the luminous layer;
an electron injection layer is arranged on the electron transport layer;
a cathode is arranged on the electron injection layer;
wherein the hole transport layer comprises the organic electroluminescent material of claim 1 or 2.
4. The organic electroluminescent device according to claim 3, wherein the hole transport layer comprises:
a first hole transport layer and a second hole transport layer;
wherein the first hole transport layer is disposed on the hole injection layer;
the second hole transport layer is disposed on the first hole transport layer;
the light emitting layer is disposed on the second hole transport layer.
5. The organic electroluminescent device according to claim 4, wherein the first hole transport layer or the second hole transport layer comprises the organic electroluminescent material according to claim 1 or 2.
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