CN110183332B - Aromatic derivative containing polycyclic alkane and organic electroluminescent device containing aromatic derivative - Google Patents

Aromatic derivative containing polycyclic alkane and organic electroluminescent device containing aromatic derivative Download PDF

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CN110183332B
CN110183332B CN201910523543.4A CN201910523543A CN110183332B CN 110183332 B CN110183332 B CN 110183332B CN 201910523543 A CN201910523543 A CN 201910523543A CN 110183332 B CN110183332 B CN 110183332B
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organic electroluminescent
electroluminescent device
carbon atoms
transport layer
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马天天
冯震
杨雷
李红燕
沙荀姗
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Shaanxi Lighte Optoelectronics Material Co Ltd
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Abstract

The invention relates to an aromatic derivative containing polycyclic alkane and an organic electroluminescent device containing the derivative, and the structure of the aromatic derivative is shown as the following chemical formula I:

Description

Aromatic derivative containing polycyclic alkane and organic electroluminescent device containing aromatic derivative
Technical Field
The invention belongs to the technical field of electroluminescence, and particularly relates to an aromatic derivative containing polycyclic alkane and an organic electroluminescent device containing the aromatic derivative.
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 general, when an organic electroluminescent device is driven at a high temperature, problems such as an increase in driving voltage, a decrease in light emitting efficiency, and a reduction in lifetime occur, resulting in a decrease in performance of the organic electroluminescent device. In order to solve the above problems, many materials have come to be used. For example: CN201680002336.1 relates to an adamantane derivative and an organic electroluminescent device thereof, which comprises a substrate, a cathode evaporated on the substrate, an anode, and an organic layer evaporated between the cathode and the anode, wherein the organic layer comprises a hole transport layer comprising a structure
Figure BDA0002097456590000011
An adamantane derivative.
At present, although a large number of organic electroluminescent materials with excellent performance have been developed, the technology still has many problems, such as that in order to improve the luminous efficiency, an appropriate organic layer is required to surround triplet excitons in an organic electroluminescent device; in order to avoid the problems of driving voltage rise, light emitting efficiency reduction, life shortening and the like when the device is driven in a high-temperature use environment, how to design a new material with better performance for adjustment is to achieve the effects of reducing voltage, improving efficiency and prolonging life of all devices, and the problems to be solved by the technical staff in the field are always urgent.
Disclosure of Invention
The present invention has been made to overcome the problems of the prior art, and an object of the present invention is to provide an aromatic derivative comprising a polycyclic alkane, which can be used as a hole injection layer, a hole transport layer, an electron blocking layer, etc. in an organic electroluminescent device, having a low driving voltage, high luminous efficiency, and a long life span, and an organic electroluminescent device comprising the same.
The technical scheme adopted by the invention is as follows: the aromatic derivative has the following structure shown in the chemical formula I:
Figure BDA0002097456590000021
wherein Ar is1One selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 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;
Ar2and Ar3The same or different, each independently selected from substituted or unsubstituted aryl with 6-40 carbon atoms, substituted or unsubstituted heteroaryl with 1-40 carbon atoms, substituted or unsubstituted alkyl with 1-35 carbon atoms, substituted or unsubstituted alkenyl with 2-35 carbon atoms, substituted or unsubstituted alkynyl with 2-35 carbon atoms, substituted or unsubstituted cycloalkyl with 3-35 carbon atoms, substituted or unsubstituted heterocycloalkyl with 2-35 carbon atoms, substituted or unsubstituted aralkyl with 7-40 carbon atoms, and substituted or unsubstituted heteroaralkyl with 2-40 carbon atoms;
a is a polycyclic alkane containing a six-membered ring, and n is an integer of 1 or more.
Further, a is selected from the following structures:
Figure BDA0002097456590000022
Figure BDA0002097456590000023
is a six-membered ring cycloalkyl group containing Ar1A broken portion of the formed single bond.
Further, the substitution is by deuterium, cyano group, nitro group, halogen, hydroxyl group, alkyl group having 1 to 40 carbon atoms, cycloalkyl group having 3 to 40 carbon atoms, alkenyl group having 2 to 40 carbon atoms, alkynyl group having 2 to 40 carbon atoms, heterocycloalkyl group having 2 to 40 carbon atoms, aralkyl group having 7 to 40 carbon atoms, heteroaralkyl group having 2 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, heteroaryl group having 1 to 40 carbon atoms, alkoxy group having 1 to 40 carbon atoms, alkylamino group having 1 to 40 carbon atoms, arylamino group having 6 to 40 carbon atoms, alkylthio group having 1 to 40 carbon atoms, aralkylamino group having 7 to 40 carbon atoms, heteroaralkylamino group having 1 to 24 carbon atoms, substituted alkyl group having 1 to 40 carbon atoms, cycloalkyl group having 3 to 40 carbon atoms, cycloalkyl group having 2 to 40 carbon atoms, alkenyl group having 2 to 40 carbon atoms, aralkyl group having 1 to 24 carbon atoms, an alkylsilyl group having 1-45 carbon atoms, an arylsilyl group having 6-50 carbon atoms, an aryloxy group having 6-30 carbon atoms or an arylthio group having 6-30 carbon atoms, in place of at least one hydrogen of the substituents or compounds.
Further, Ar1Selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted indenyl, substituted or unsubstituted azulenyl
Figure BDA0002097456590000032
And one of a group, a pyrimidine substituted or unsubstituted pyridyl group, and a substituted or unsubstituted pyridyl group.
Further, Ar1A and N are connected by a single bond.
Further, the aromatic derivatives include:
Figure BDA0002097456590000031
Figure BDA0002097456590000041
Figure BDA0002097456590000051
Figure BDA0002097456590000061
Figure BDA0002097456590000071
Figure BDA0002097456590000081
Figure BDA0002097456590000091
an organic electroluminescent device comprising an anode and a cathode, and one or more organic layers interposed between the anode and the cathode, at least one of the organic layers comprising an aromatic derivative as defined in any one of the above.
Further, the organic layer comprises a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer which are arranged in sequence from the anode to the cathode; the cathode is provided with a covering layer.
Further, the hole transport layer contains an aromatic derivative.
Further, the hole transport layer includes: a first hole transport layer and a second hole transport layer;
the first hole transport layer is arranged on the hole injection layer; the second hole transport layer is arranged on the first hole transport layer; the light emitting layer is positioned on the second hole transport layer.
Compared with the prior art, the invention has the following beneficial effects:
the compound is an aromatic derivative which takes six-membered cycloalkane as a base and contains polycyclic alkane as a skeleton, and compared with common substituent, straight-chain alkane or monocycloparaffin, the polycyclic alkane containing six-membered ring has more excellent stability and high heat resistance; the cyclic alkane has a highly complex three-dimensional structure, so that energy loss caused by molecular rotation, motion and vibration can be greatly reduced compared with common substituents such as aryl, and meanwhile, the three-dimensional structure of the cyclic alkane can form a stable condensed ring; the partially asymmetric polycyclic alkane has the characteristics of reducing the molecular symmetry, thereby reducing the molecular stacking to improve the film forming property of the material. Therefore, these polycyclic alkanes containing a six-membered ring can improve the stability of the organic layer in the organic electroluminescent device.
The aromatic derivative is used in an organic electroluminescent device and can show light wave wavelength within the range of 450-780nm, the polycyclic alkane derivative combines functional characteristic molecules with the characteristics of hole injection, hole transmission, electron blocking and the like to form the polycyclic alkane aromatic derivative containing six-membered rings, and the polycyclic alkane aromatic derivative has excellent stability and high heat resistance when being used as the organic electroluminescent device, compared with a device without the aromatic derivative, the driving voltage, the current efficiency, the external quantum efficiency and the service life of the aromatic derivative are obviously improved, the voltage is reduced by about 1-2V, the luminous efficiency is improved by at least about 30 percent, and the service life can be prolonged by 3.6 times.
Drawings
FIG. 1 is a schematic structural diagram of an aromatic derivative according to the present invention;
fig. 2 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention;
fig. 3 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.
Detailed Description
In the present invention, the hole characteristics refer to characteristics that holes formed in the anode are easily injected into the light emitting layer and are transported in the light emitting layer due to conduction characteristics according to HOMO levels.
The electron characteristics refer to characteristics that electrons formed in the cathode are easily injected into the light emitting layer and are transported in the light emitting layer due to conduction characteristics according to the LUMO level.
Compounds for use in organic electroluminescent devices include compounds which may function in emitting light or injecting and/or transporting electrons and may also act as light-emitting hosts containing suitable dopants. In other words, the compound for an organic electroluminescent device may be used as a phosphorescent or fluorescent host material, a blue light emitting dopant material, or an electron transport material.
The compound for an organic electroluminescent device according to one embodiment of the present invention is used as an organic layer, and it may improve life characteristics, efficiency characteristics, electrochemical stability, and thermal stability of the organic electroluminescent device and reduce driving voltage.
Another aspect of the present invention is to provide an organic light emitting device including an aromatic derivative of the polycyclic alkane, which has a lower driving voltage, higher light emitting efficiency, and a long life span.
The aromatic derivative of the invention is triarylamine containing polycyclic alkane derived based on six-membered cycloalkane in the structure of the compound. The invention uses polycyclic alkane containing six-membered ring as hole injection and hole transmission material of organic electroluminescence, compared with general substituent, straight chain alkane or monocycloparaffin, polycyclic alkane containing six-membered ring has more excellent stability and high heat resistance. In particular, cyclic alkanes having highly complex three-dimensional structures such as bicyclo [2.2.2] octane, bicyclo [2.2.1] heptane, tricyclo [3.3.1.13,6] octane, tricyclo [3.3.1.13, 7] octane, tricyclo [ 3.3.1.03, 7] nonane, and tricyclo [4.3.1.03,8] decane can significantly reduce energy loss due to molecular rotation, motion, and vibration, as compared with general substituents such as aryl groups. At the same time, its steric structure also enables it to form stable fused rings. Some of the asymmetric polycycloalkanes, such as tricyclo [3.3.1.13, 7] octane, tricyclo [ 3.3.1.03, 7] nonane, etc., have the characteristics of reducing the molecular symmetry and thus reducing the molecular stacking to improve the film-forming property of the material. Therefore, these polycyclic alkanes containing a six-membered ring can improve the stability of the organic layer in the organic electroluminescent device.
The aromatic derivative has a structure shown in a chemical formula I:
Figure BDA0002097456590000111
wherein Ar is1One selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 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; ar (Ar)1A and N are connected by a single bond.
Preferably, Ar1Selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted indenyl, substituted or unsubstituted azulenyl
Figure BDA0002097456590000113
And one of a group, a pyrimidine substituted or unsubstituted pyridyl group, and a substituted or unsubstituted pyridyl group.
Ar2、Ar3The same or different, each independently selected from substituted or unsubstituted aryl with 6-40 carbon atoms, substituted or unsubstituted heteroaryl with 1-40 carbon atoms, substituted or unsubstituted alkyl with 1-35 carbon atoms, substituted or unsubstituted alkenyl with 2-35 carbon atoms, substituted or unsubstituted alkynyl with 2-35 carbon atoms, substituted or unsubstituted cycloalkyl with 3-35 carbon atoms, substituted or unsubstituted heterocycloalkyl with 2-35 carbon atoms, substituted or unsubstituted aralkyl with 7-40 carbon atoms, and substituted or unsubstituted heteroaralkyl with 2-40 carbon atoms;
a is a polycyclic alkane comprising a six-membered ring selected from the following structures:
Figure BDA0002097456590000112
Figure BDA0002097456590000121
n is an integer of 1 or more.
Figure BDA0002097456590000122
Is a six-membered ring cycloalkyl group containing Ar1A broken portion of the formed single bond.
"substituted" means substituted with deuterium, cyano group, nitro group, halogen, hydroxy group, alkyl group having 1 to 40 carbon atoms, cycloalkyl group having 3 to 40 carbon atoms, alkenyl group having 2 to 40 carbon atoms, alkynyl group having 2 to 40 carbon atoms, heterocycloalkyl group having 2 to 40 carbon atoms, aralkyl group having 7 to 40 carbon atoms, heteroaralkyl group having 2 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, heteroaryl group having 1 to 40 carbon atoms, alkoxy group having 1 to 40 carbon atoms, alkylamino group having 1 to 40 carbon atoms, arylamino group having 6 to 40 carbon atoms, alkylthio group having 1 to 40 carbon atoms, aralkylamino group having 7 to 40 carbon atoms, heteroaralkylamino group having 1 to 24 carbon atoms, heteroarylamino group having 1 to 24 carbon atoms, or a pharmaceutically acceptable salt thereof, In place of A, Ar, an alkylsilyl group having 1-45 carbon atoms, an arylsilyl group having 6-50 carbon atoms, an aryloxy group having 6-30 carbon atoms or an arylthio group having 6-30 carbon atoms is substituted1、Ar2And Ar3At least one hydrogen of the compound or substituent in (1), A, Ar1、Ar2And Ar3The substituents of (A) are the same or different.
In the present specification, when a specific definition is not otherwise provided, "hetero" means that 1 to 3 hetero atoms selected from the group consisting of B, N, O, S and P are included in one functional group and the rest are carbon.
The alkyl group may be a "saturated alkyl group" without any double or triple bonds. The alkyl group may be a branched, straight chain or cyclic alkyl group.
"alkenyl group" refers to a functional group having at least one carbon-carbon double bond of at least two carbons, and "alkynyl group" refers to a functional group having at least one carbon-carbon triple bond of at least two carbons.
"aryl group" includes monocyclic or fused polycyclic (i.e., rings that share adjacent pairs of carbon atoms) groups.
"heteroaryl group" means an aryl group that includes 1 to 3 heteroatoms selected from the group consisting of N, O, S and P, with the remainder being carbon. When the heteroaryl group is a fused ring, each ring may include 1 to 3 heteroatoms.
Hereinafter, the organic electroluminescent device is specifically described.
An organic electroluminescent device according to a further embodiment of the present invention includes an anode, a cathode, and at least one or more organic layers interposed between the anode and the cathode, and at least one organic layer may include an aromatic derivative for an organic electroluminescent device according to an embodiment of the present invention.
Fig. 1 and 2 are sectional views of an organic electroluminescent device including an aromatic derivative for an organic electroluminescent device according to an embodiment of the present invention.
Referring to fig. 1 and 2, an organic electroluminescent device according to an embodiment and includes at least one organic layer interposed between an anode and a cathode.
The anode comprises an anode material, which is preferably a material with a large work function that facilitates hole injection into the organic layer. Specific examples of the anode material include: metals such as nickel, platinum, vanadium, chromium, copper, zinc and gold or alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combined metals and oxides, e.g. ZnO: Al or SnO2Sb; or a conductive polymer such as poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDT), polypyrrole, and polyaniline, but are not limited thereto. Preferably, a transparent electrode including Indium Tin Oxide (ITO) as an anode is included.
The cathode includes a cathode material, which is a material having a small work function that facilitates electron injection into the organic layer. Specific examples of the cathode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silverTin and lead or alloys thereof; or a multilayer material such as LiF/Al, Liq/Al, LiO2Al, LiF/Ca, LiF/Al and BaF2But not limited thereto,/Ca. Preferably, a metal electrode comprising aluminum is included as a cathode.
Referring to fig. 2, the organic layer includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer sequentially arranged in a direction from an anode to a cathode; referring to fig. 3, the hole transport layer includes: the first hole transport layer is arranged on the hole injection layer; the second hole transport layer is arranged on the first hole transport layer; the light-emitting layer is located on the second hole transport layer, and the first hole transport layer and the second hole transport layer both contain aromatic derivatives.
The present invention is further illustrated by the following examples (cycloalkane + arylamine). However, the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Synthesis of Compound 1
Figure BDA0002097456590000131
Adding bicyclo [2,2,1] heptane (10.0g,104.0mmol) and trifluoroacetic acid (100mL) into a 250mL round-bottom flask, adding concentrated nitric acid (0.3g) under stirring, heating to 45-50 ℃, and stirring for 4 hours in an air atmosphere; trifluoroacetic acid was removed under reduced pressure, and 10% potassium hydroxide ethanol solution (90mL) was added to the remaining mixture, followed by stirring for 1 hour; removing ethanol under reduced pressure, adding dichloromethane into the bottle, washing with water twice, drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; the product was purified by silica gel column chromatography using dichloromethane/n-heptane as eluent to give intermediate 1-A-1(4.7 g; 40%) as white crystals.
Figure BDA0002097456590000132
Adding the intermediate I-A-1(4.7g,41.9mmol), 2-bromo-9, 9-dimethylfluorene (11.4g,41.9mmol) and dichloromethane (50mL) into a 100mL round-bottom flask, and dropwise adding trifluoromethanesulfonic acid (9.4g,62.9mmol) at-35 to-40 ℃ under the protection of nitrogen; after the dropwise addition, stirring at low temperature for 4 hours, heating to room temperature, and slowly dropwise adding a 10% sodium hydroxide aqueous solution into the reaction solution until the solution is neutral; separating an organic phase, washing the organic phase twice by using water, drying by using anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; the product was purified by silica gel column chromatography using n-heptane as eluent to give intermediate I-A (7.8 g; 51%) as a white solid.
Figure BDA0002097456590000141
4-bromobiphenyl (10.0g,42.9mmol), 2-amino-9, 9-dimethylfluorene (9.9g,47.2mmol), tris (dibenzylideneacetone) dipalladium (0.4g,0.4mmol), 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (0.4g,0.9mmol) and sodium tert-butoxide (6.2g,64.4mmol) were added to toluene (100mL), heated to 105 ℃ under nitrogen and stirred for 1 hour; cooling to room temperature, washing the reaction solution twice 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 I-B as a pale gray solid (12.5g, 81%).
Figure BDA0002097456590000142
Adding the intermediate I-A (7.8g,21.2mmol), the intermediate I-B (7.7g,21.2mmol), tris (dibenzylideneacetone) dipalladium (0.4g,0.4mmol), 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.3g,0.8mmol) and sodium tert-butoxide (4.1g,42.5mmol) into toluene (60mL), 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 afford compound I (6.2g, 45%) as a white solid (formula 65). Mass spectrum: m/z 648.4(M + H)+
Synthesis of Compound 2
Figure BDA0002097456590000143
Adding bicyclo [2,2,2] octane (10.0g,90.7mmol) and trifluoroacetic acid (80mL) into a 250mL round-bottom flask, adding concentrated nitric acid (0.2g) under the condition of stirring, heating to 45-50 ℃, and stirring for 3 hours in an air atmosphere; trifluoroacetic acid was removed under reduced pressure, and 10% potassium hydroxide ethanol solution (80mL) was added to the remaining mixture, followed by stirring for 1 hour; removing ethanol under reduced pressure, adding dichloromethane into the bottle, washing with water twice, drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; the product was purified by silica gel column chromatography using dichloromethane/n-heptane as eluent to give intermediate II-A-1(5.0 g; 44%) as a white solid.
Figure BDA0002097456590000151
Adding the intermediate II-A-1(5.0g,39.6mmol), 4-bromobiphenyl (9.2g,39.6mmol) and dichloromethane (50mL) into a 100mL round-bottom flask, and dropwise adding trifluoromethanesulfonic acid (8.9g,59.4mmol) at-20 to-15 ℃ under the protection of nitrogen; after the dropwise addition, keeping stirring at low temperature for 6 hours, heating to room temperature, and slowly dropwise adding a 10% sodium hydroxide aqueous solution into the reaction liquid until the reaction liquid is neutral; separating an organic phase, washing the organic phase twice by using water, drying by using anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; the product was purified by silica gel column chromatography using n-heptane as eluent to give intermediate II-A (6.5 g; 48%) as white crystals.
Figure BDA0002097456590000152
2-bromobiphenyl (10.0g,42.9mmol), 2-amino-9, 9-dimethylfluorene (9.9g,47.2mmol), tris (dibenzylideneacetone) dipalladium (0.4g,0.4mmol), 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (0.4g,0.9mmol) and sodium tert-butoxide (6.2g,64.4mmol) were added to toluene (100mL), heated to 105 ℃ under nitrogen and stirred for 2 hours; cooling to room temperature, washing the reaction solution twice 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 (11.0g, 71%).
Figure BDA0002097456590000153
Adding the intermediate II-A (6.5g,19.0mmol), the intermediate II-B (6.9g,19.0mmol), tris (dibenzylideneacetone) dipalladium (0.3g,0.4mmol), 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.3g,0.8mmol) and sodium tert-butoxide (3.7,38.1mmol) into toluene (50mL), 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/ethyl acetate system to give compound II (7.6g, 64%) as a white solid (formula 58). Mass spectrum: 622.3(M + H) M/z+
Synthesis of Compound 3
Figure BDA0002097456590000161
Adding bicyclo [3.2.1] octane (8.0g,72.6mmol) and trifluoroacetic acid (100mL) into a 250mL round-bottom flask, adding concentrated nitric acid (0.5g) under the condition of stirring, heating to 50-55 ℃, and stirring for 3 hours in an air atmosphere; trifluoroacetic acid was removed under reduced pressure, and 10% potassium hydroxide ethanol solution (80mL) was added to the remaining mixture, followed by stirring for 1 hour; removing ethanol under reduced pressure, adding dichloromethane into the bottle, washing with water twice, drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; the product was purified by silica gel column chromatography using ethyl acetate/n-heptane as eluent to give the white needle-like intermediate III-A-1(4.5 g; 49%).
Figure BDA0002097456590000162
Adding the intermediate III-A-1(4.5g,35.7mmol), 2-bromo-9, 9-dimethylfluorene (9.7g,35.7mmol) and dichloromethane (50mL) into a 100mL round-bottom flask, and dropwise adding trifluoromethanesulfonic acid (8.0g,53.5mmol) at-20 to-15 ℃ under the protection of nitrogen; after the dropwise addition, stirring at low temperature for 3 hours, heating to room temperature, and slowly dropwise adding a 10% sodium hydroxide aqueous solution into the reaction solution until the solution is neutral; separating an organic phase, washing the organic phase twice by using water, drying by using anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; the product was purified by silica gel column chromatography using n-heptane as eluent to give intermediate III-A (8.2 g; 60%) as a pale gray solid.
Figure BDA0002097456590000163
2-bromobiphenyl (10.0g,42.9mmol), 4-aminobiphenyl (8.0g,47.2mmol), tris (dibenzylideneacetone) dipalladium (0.4g,0.4mmol), 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (0.4g,0.9mmol) and sodium tert-butoxide (6.2g,64.4mmol) were added to toluene (100mL), heated to 105-; cooling to room temperature, washing the reaction solution twice 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 III-B as a white solid (12.1g, 88%).
Figure BDA0002097456590000171
Adding the intermediate III-A (8.2g,21.5mmol), the intermediate III-B (6.9g,21.5mmol), the tris (dibenzylideneacetone) dipalladium (0.4g,0.4mmol), the 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.4g,0.9mmol) and the sodium tert-butoxide (4.1,43.0mmol) into toluene (70mL), 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 give compound III (7.1g, 53%) as a white solid (formula 56). Mass spectrum: 622.3(M + H) M/z+
Synthesis of Compound 4
Figure BDA0002097456590000172
Adding bicyclo [3.3.1] nonane (10.0g,80.5mmol) and trifluoroacetic acid (100mL) into a 50mL round-bottom flask, adding nitric acid (0.2g) under stirring, heating to 45-50 ℃, and stirring for 8 hours in an air atmosphere; trifluoroacetic acid was removed under reduced pressure, and 10% potassium hydroxide ethanol solution (80mL) was added to the remaining mixture, followed by stirring for 0.5 hour; removing ethanol under reduced pressure, adding dichloromethane into the bottle, washing with water twice, drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; the product was purified by silica gel column chromatography using ethyl acetate/n-heptane as eluent to give intermediate IV-A-1(3.9 g; 35%) as white crystals.
Figure BDA0002097456590000173
Adding the intermediate IV-A-1(3.9g,27.8mmol), bromobenzene (4.4g,27.8mmol) and dichloromethane (40mL) into a 100mL round-bottom flask, and dropwise adding trifluoromethanesulfonic acid (6.3g,41.7mmol) at-25 to-20 ℃ under the protection of nitrogen; after the dropwise addition, stirring at low temperature for 4 hours, heating to room temperature, and slowly dropwise adding a 10% sodium hydroxide aqueous solution into the reaction solution until the solution is neutral; separating an organic phase, washing the organic phase twice by using water, drying by using anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; the product was purified by silica gel column chromatography using n-heptane as eluent to give intermediate IV-A (5.1 g; 66%) as a pale yellow solid.
Figure BDA0002097456590000181
2-bromo-9-phenylcarbazole (15.0g,46.6mmol), 4-aminobiphenyl (8.7g,51.2mmol), tris (dibenzylideneacetone) dipalladium (0.4g,0.5mmol), 2-dicyclohexylphosphonium-2, 4, 6-triisopropylbiphenyl (0.4g,0.9mmol) and sodium tert-butoxide (6.7g,69.8mmol) were added to toluene (150mL), heated to 105 ℃ under nitrogen and stirred for 1.5 hours; cooling to room temperature, washing the reaction solution twice 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 IV-B as a white solid (14.0g, 73%).
Figure BDA0002097456590000182
Adding the intermediate IV-A (5.1g,18.3mmol), the intermediate IV-B (7.5g,18.3mmol), tris (dibenzylideneacetone) dipalladium (0.3g,0.4mmol), 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.3g,0.7mmol) and sodium tert-butoxide (3.5,36.5mmol) into toluene (40mL), 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/ethyl acetate system to give compound IV (8.0g, 72%) as a white solid (formula 78). Mass spectrum: m/z 609.3(M + H)+
Synthesis of Compound 5
Figure BDA0002097456590000183
Adding bicyclo [4.3.0] nonane (10.0g,80.5mmol) and trifluoroacetic acid (120mL) into a 50mL round-bottom flask, adding nitric acid (0.5g) under stirring, heating to 40-45 ℃, and stirring for 6 hours in an air atmosphere; trifluoroacetic acid was removed under reduced pressure, and 10% potassium hydroxide ethanol solution (100mL) was added to the remaining mixture, followed by stirring for 0.5 hour; removing ethanol under reduced pressure, adding dichloromethane into the bottle, washing with water twice, drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; the product was purified by silica gel column chromatography using dichloromethane/n-heptane as eluent to give intermediate V-A-1(5.7 g; 51%) as a pale yellow solid.
Figure BDA0002097456590000191
Adding the intermediate V-A-1(5.7g,40.7mmol), 4-bromobiphenyl (9.5g,40.7mmol) and dichloromethane (60mL) into a 100mL round-bottom flask, and dropwise adding trifluoromethanesulfonic acid (9.2g,61.0mmol) at-20 to-15 ℃ under the protection of nitrogen; after the dropwise addition, keeping stirring at low temperature for 6 hours, heating to room temperature, and slowly dropwise adding a 10% sodium hydroxide aqueous solution into the reaction liquid until the reaction liquid is neutral; separating an organic phase, washing the organic phase twice by using water, drying by using anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; the product was purified by silica gel column chromatography using n-heptane as eluent to give intermediate V-A (6.4 g; 44%) as a white solid.
Figure BDA0002097456590000192
2-bromo-9, 9-dimethylfluorene (12.0g,43.9mmol), 2-amino-9, 9-dimethylfluorene (10.1g,48.3mmol), tris (dibenzylideneacetone) dipalladium (0.4g,0.4mmol), 2-dicyclohexyl-phosphorus-2, 4, 6-triisopropylbiphenyl (0.4g,0.9mmol) and sodium tert-butoxide (6.3g,65.9mmol) were added to toluene (120mL), heated to 105-fold 110 ℃ under nitrogen protection, and stirred for 2.5 hours; cooling to room temperature, washing the reaction solution twice 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 V-B as a grey solid (15.2g, 84%).
Figure BDA0002097456590000193
Adding the intermediate V-A (6.4g,18.0mmol), the intermediate V-B (7.2g,18.0mmol), tris (dibenzylideneacetone) dipalladium (0.3g,0.4mmol), 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.3g,0.7mmol) and sodium tert-butoxide (3.5,36.0mmol) into toluene (50mL), 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 toluene/n-heptane system to give compound V (6.8g, 56%) as a white solid (formula 75). Mass spectrum: m/z 676.4(M + H)+
Synthesis of Compound 6
Figure BDA0002097456590000201
Adding bicyclo [4.4.0] decane (11.0g,79.6mmol) and trifluoroacetic acid (110mL) into a 250mL round-bottom flask, adding nitric acid (0.3g) under the condition of stirring, heating to 50-55 ℃, and stirring for 4 hours in an air atmosphere; trifluoroacetic acid was removed under reduced pressure, and 10% potassium hydroxide ethanol solution (90mL) was added to the remaining mixture, followed by stirring for 1 hour; removing ethanol under reduced pressure, adding dichloromethane into the bottle, washing with water twice, drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; the product was purified by column chromatography on silica gel using dichloromethane/n-heptane as eluent to give intermediate VI-A-1(4.4 g; 36%) as a white solid.
Figure BDA0002097456590000202
Adding the intermediate VI-A-1(4.4g,28.5mmol), bromobenzene (4.5g,28.5mmol) and dichloromethane (45mL) into a 100mL round-bottom flask, and dropwise adding trifluoromethanesulfonic acid (6.4g,42.8mmol) at-15 to-10 ℃ under the protection of nitrogen; after the dropwise addition, stirring at low temperature for 8 hours, heating to room temperature, and slowly dropwise adding a 10% sodium hydroxide aqueous solution into the reaction solution until the solution is neutral; separating an organic phase, washing the organic phase twice by using water, drying by using anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; the product was purified by silica gel column chromatography using n-heptane as eluent to give intermediate VI-A (5.1 g; 61%) as a white powder.
Figure BDA0002097456590000203
3-bromodibenzofuran (10.0g,40.5mmol), 4-aminobiphenyl (7.5g,44.5mmol), tris (dibenzylideneacetone) dipalladium (0.4g,0.4mmol), 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (0.4g,0.8mmol) and sodium tert-butoxide (5.8g,60.7mmol) were added to toluene (100mL), heated to 105-phase 110 ℃ under nitrogen protection, and stirred for 1 hour; cooling to room temperature, washing the reaction solution twice 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 VI-B as a white solid (10.4g, 77%).
Figure BDA0002097456590000211
Adding the intermediate VI-A (5.1g,17.4mmol), the intermediate VI-B (5.8g,17.4mmol), tris (dibenzylideneacetone) dipalladium (0.3g,0.3mmol), 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.3g,0.7mmol) and sodium tert-butoxide (3.3,34.8mmol) into toluene (40mL), 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 give compound VI (6.6g, 69%) as a white solid (formula 68). Mass spectrum: 548.3(M + H) equal to M/z+
Synthesis of Compound 7
Figure BDA0002097456590000212
The tricyclic [3.3.1.0 ]3,7]Adding nonane (10.0g,81.8mmol) and trifluoroacetic acid (100mL) into a 250mL round-bottom flask, adding nitric acid (0.2g) under stirring, heating to 45-50 ℃, and stirring for 6 hours in an air atmosphere; trifluoroacetic acid was removed under reduced pressure, and 10% potassium hydroxide ethanol solution (100mL) was added to the remaining mixture, followed by stirring for 1.5 hours; removing ethanol under reduced pressure, adding dichloromethane into the bottle, washing with water twice, drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; the product was purified by silica gel column chromatography using dichloromethane/n-heptane as eluent to give intermediate VII-A-1(5.1 g; 45%) as a white powder.
Figure BDA0002097456590000213
Adding the intermediate VII-A-1(5.1g,36.9mmol), 4-bromobiphenyl (8.6g,36.9mmol) and dichloromethane (50mL) into a 100mL round-bottom flask, and dropwise adding trifluoromethanesulfonic acid (8.3g,55.4mmol) at-20 to-15 ℃ under the protection of nitrogen; after the dropwise addition, keeping stirring at low temperature for 6 hours, heating to room temperature, and slowly dropwise adding a 10% sodium hydroxide aqueous solution into the reaction liquid until the reaction liquid is neutral; separating an organic phase, washing the organic phase twice by using water, drying by using anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; the product was purified by silica gel column chromatography using n-heptane as eluent to give intermediate VII-A as a pale gray solid (6.9 g; 53%).
Figure BDA0002097456590000221
3-bromodibenzofuran (10.0g,40.5mmol), 2-bromo-9, 9-dimethylfluorene (9.3g,44.5mmol), tris (dibenzylideneacetone) dipalladium (0.4g,0.4mmol), 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (0.4g,0.8mmol) and sodium tert-butoxide (5.8g,60.7mmol) were added to toluene (100mL), heated to 105 ℃ under nitrogen protection, and stirred for 2 hours; cooling to room temperature, washing the reaction solution twice 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 VII-B as a pale yellow solid (12.1g, 80%).
Figure BDA0002097456590000222
Adding the intermediate VII-A (6.9g,19.5mmol), the intermediate VII-B (7.3g,19.5mmol), tris (dibenzylideneacetone) dipalladium (0.4g,0.4mmol), 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.3g,0.8mmol) and sodium tert-butoxide (3.8,39.1mmol) into toluene (60mL), 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/ethyl acetate system to give compound VII (7.0g, 55%) as a white solid (formula 76). Mass spectrum: m/z 648.3(M + H)+
Synthesis of Compound 8
Figure BDA0002097456590000223
The tricyclic [3.3.1.13,6]Adding decane (10.0g,73.4mmol) and trifluoroacetic acid (100mL) into a 250mL round-bottom flask, adding nitric acid (0.3g) under the stirring condition, heating to 45-50 ℃, and stirring for 4 hours in an air atmosphere; trifluoroacetic acid was removed under reduced pressure, and 10% potassium hydroxide ethanol solution (80mL) was added to the remaining mixture, followed by stirring for 1 hour; removing ethanol under reduced pressure, adding dichloromethane into the bottle, washing with water twice, drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; the product was purified by silica gel column chromatography using ethyl acetate/n-heptane as eluent to give intermediate VIII-A-1(4.6 g; 41%) as a pale yellow powder.
Figure BDA0002097456590000231
Adding the intermediate VIII-A-1(4.6g,30.2mmol), bromobenzene (4.7g,30.2mmol) and dichloromethane (50mL) into a 100mL round-bottom flask, and dropwise adding trifluoromethanesulfonic acid (6.8g,45.3mmol) at-20 to-15 ℃ under the protection of nitrogen; after the dropwise addition, stirring at low temperature for 8 hours, heating to room temperature, and slowly dropwise adding a 10% sodium hydroxide aqueous solution into the reaction solution until the solution is neutral; separating an organic phase, washing the organic phase twice by using water, drying by using anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; the product was purified by silica gel column chromatography using n-heptane as eluent to give intermediate VIII-A (6.0 g; 68%) as a white solid.
Figure BDA0002097456590000232
3-bromodibenzothiophene (12.0g,45.6mmol), 4-aminobiphenyl (8.5g,50.2mmol), tris (dibenzylideneacetone) dipalladium (0.4g,0.5mmol), 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (0.4g,0.9mmol) and sodium tert-butoxide (6.6g,68.4mmol) were added to toluene (120mL), heated to 105-phase 110 ℃ under nitrogen protection, and stirred for 1.5 hours; cooling to room temperature, washing the reaction solution twice 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 give intermediate VIII-B as a pale brown solid (13.9g, 87%).
Figure BDA0002097456590000233
Adding the intermediate VIII-A (6.0g,20.6mmol), the intermediate VIII-B (7.2g,20.6mmol), tris (dibenzylideneacetone) dipalladium (0.4g,0.4mmol), 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.3g,0.8mmol) and sodium tert-butoxide (4.0,41.2mmol) into toluene (50mL), 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 toluene/n-heptane system to give compound VIII (6.8g, 59%) as a white solid (formula 66). Mass spectrum: m/z 562.3(M + H)+
Synthesis of Compound 9
Figure BDA0002097456590000241
Will tricyclic [4.3.1.0 ]3,8]Adding decane (12.0g,88.1mmol) and trifluoroacetic acid (120mL) into a 250mL round-bottom flask, adding nitric acid (0.5g) under the condition of stirring, heating to 50-55 ℃, and stirring for 5 hours in an air atmosphere; trifluoroacetic acid was removed under reduced pressure, and 10% potassium hydroxide ethanol solution (100mL) was added to the remaining mixture, followed by stirring for 0.5 hour; removing ethanol under reduced pressure, adding dichloromethane into the bottle, washing with water twice, drying with anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; the product was purified by silica gel column chromatography using ethyl acetate/n-heptane as eluent to give intermediate IX-A-1(6.0 g; 45%) as a pale yellow solid.
Figure BDA0002097456590000242
Adding the intermediate VIII-A-1(6.0g,39.4mmol), 2-bromo-9, 9-dimethylfluorene (10.8g,39.4mmol) and dichloromethane (60mL) into a 100mL round-bottom flask, and dropwise adding trifluoromethanesulfonic acid (8.9g,59.1mmol) at-35-30 ℃ under the protection of nitrogen; after the dropwise addition, stirring at low temperature for 3 hours, heating to room temperature, and slowly dropwise adding a 10% sodium hydroxide aqueous solution into the reaction solution until the solution is neutral; separating an organic phase, washing the organic phase twice by using water, drying by using anhydrous magnesium sulfate, and removing the solvent under reduced pressure to obtain a crude product; the product was purified by silica gel column chromatography using n-heptane as eluent to give intermediate IX-A (9.1 g; 57%) as a white solid.
Figure BDA0002097456590000243
2-bromonaphthalene (10.0g,48.3mmol), 4-aminobiphenyl (9.0g,53.1mmol), tris (dibenzylideneacetone) dipalladium (0.4g,0.5mmol), 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (0.5g,1.0mmol) and sodium tert-butoxide (7.0g,72.4mmol) were added to toluene (100mL), heated to 105-phase 110 ℃ under nitrogen protection, and stirred for 0.5 hour; cooling to room temperature, washing the reaction solution twice 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 IX-B (10.8g, 76%) as a white solid.
Figure BDA0002097456590000251
Adding the intermediate IX-A (9.1g,22.3mmol), the intermediate IX-B (6.6g,22.3mmol), the tris (dibenzylideneacetone) dipalladium (0.4g,0.4mmol), the 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.4g,0.9mmol) and the sodium tert-butoxide (4.3,44.7mmol) into toluene (70mL), 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/ethyl acetate system to give compound IX (7.5g, 54%) as a white solid (formula 60). Mass spectrum: 622.3(M + H) M/z+
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 BDA0002097456590000252
The ITO substrate (manufactured by Corning) of (1) was cut into a size of 40mm × 40mm × 0.7mm, 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 BDA0002097456590000253
And NPB is deposited on the hole injection layer to form a thickness of
Figure BDA0002097456590000254
And a first hole transport layer (HT 1).
Vacuum evaporating compound 1 on the first hole transport layer to a thickness of
Figure BDA0002097456590000255
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)2Is formed to a thickness of
Figure BDA0002097456590000256
The light emitting layer (EML).
DBimiBphen and LiQ are mixed according to the weight ratio of 1:1 and evaporated to form
Figure BDA0002097456590000257
A thick Electron Transport Layer (ETL), and depositing LiQ on the electron transport layer to form a layer with a thickness of
Figure BDA0002097456590000258
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 BDA0002097456590000259
The cathode of (1).
Further, the cathode is deposited with a thickness of
Figure BDA00020974565900002510
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 a top-emitting organic light-emitting device.
Examples 2 to 5
An organic electroluminescent device was fabricated by the same method as example 1, except that the compounds shown in table 1 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, comparative example NPD produced an organic electroluminescent device, and comparative example 2 produced an organic electroluminescent device using TPD, 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 organic electroluminescent devices obtained in examples 1 to 5 and comparative examples 1 to 3 were tested for performance
Examples Compound (I) Volt(V) Cd/A EQE T95(h) Colour(s)
Example 1 Compound 1 3.55 33.82 22.64 400 Red
Example 2 Compound 2 3.61 32.89 22.55 410 Red
Example 3 Compound 3 3.82 30.79 23.95 470 Red
Example 4 Compound 4 3.89 31.93 25.54 390 Red
Example 5 Compound 5 3.78 30.89 23.91 372 Red
Comparative example 1 NPD 4.54 26.00 19.71 210 Red
Comparative example 2 TPD 5.32 25.40 18.50 230 Red
Comparative example 3 - 4.32 18.30 14.64 189 Red
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 the second hole transport layer material of the organic electroluminescent device, the driving voltage (Vlot), the current efficiency (Cd/a), and the External Quantum Efficiency (EQE) and the lifetime (T95) were all significantly improved and the lifetime was doubled as compared with those of comparative examples 1 to 2.
Compared with the comparative example, the compound of the example is used for the organic electroluminescent device, the voltage is reduced by about 1-2V, and the luminous efficiency is improved by at least about 30%.
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).
The examples show lower driving voltage and increased efficiency compared to the comparative examples.
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 BDA0002097456590000271
The ITO substrate (manufactured by Corning) of (1) was cut into a size of 40mm × 40mm × 0.7mm, 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 BDA0002097456590000272
And a compound 6 is vacuum-evaporated on the hole injection layer to form a layer having a thickness of
Figure BDA0002097456590000273
And a first hole transport layer (HT 1).
Depositing TCTA on the first hole transport layer to a thickness of
Figure BDA0002097456590000274
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 BDA0002097456590000275
The light emitting layer (EML).
DBimiBphen and LiQ are mixed according to the weight ratio of 1:1 and evaporated to form
Figure BDA0002097456590000276
A thick Electron Transport Layer (ETL), and depositing LiQ on the electron transport layer to form a layer with a thickness of
Figure BDA0002097456590000277
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 BDA0002097456590000279
The cathode of (1).
Further, the cathode is deposited with a thickness of
Figure BDA0002097456590000278
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 9
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, the performance of the organic electroluminescent device manufactured by using the compound 7 in example 7, the organic electroluminescent device manufactured by using the compound 8 in example 8, and the organic electroluminescent device manufactured by using the compound 9 in example 9 is shown in table 2.
Comparative examples 4 to 6
In comparative examples 4 to 5, 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 examples 6 to 9 and comparative examples 4 to 6 organic electroluminescent devices test performance
Examples Compound (I) Volt(V) Cd/A EQE％ T95(h) Colour(s)
Example 6 Compound 6 4.0 6.7 14.3 200 Blue
Example 7 Compound 7 4.1 6.8 14.6 210 Blue
Example 8 Compound 8 3.9 6.9 14.9 198 Blue
Example 9 Compound 9 4.2 7.2 15.1 209 Blue
Comparative example 4 NPB 5.6 6.2 9.2 75 Blue
Comparative example 5 NPD 5.0 6.0 8.9 68 Blue
Comparative example 6 TPD 5.5 5.6 6.9 59 Blue
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.
Compared with comparative examples 4-6, the voltage of the organic electroluminescent device manufactured by using the compound of the invention, especially compound 8, is reduced by 1.1V, and the external quantum efficiency is improved by 67% compared with NPD, which is a very significant improvement for blue light devices.
For OLED devices (i.e. organic electroluminescent devices) the improvement in their effect (e.g. in EQE) is very significant even though it appears to be only a few percent on the data.
Specifically, the External Quantum Efficiency (EQE) can be calculated according to the following formula, for example, EQE is the number of photons/injected electrons emitted out of the device; for another example, EQE is the light extraction rate and internal quantum efficiency (light extraction rate less than 1).
For a blue light device, the luminescent layer is made of fluorescent material, and the fluorescent material is singlet exciton luminescent, and the internal quantum efficiency is up to 25%. When the light is emitted externally, due to other reasons such as light loss caused by a device structure such as coupling, the external quantum efficiency is lower than 25% because only 25% of excitons can be used, so that the efficiency is generally lower.
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.
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 aromatic derivative comprising a polycyclic alkane characterized by:
the aromatic derivatives include:
Figure FDA0002401467860000011
Figure FDA0002401467860000021
Figure FDA0002401467860000031
Figure FDA0002401467860000041
Figure FDA0002401467860000051
Figure FDA0002401467860000061
2. an organic electroluminescent device, characterized in that: comprising an anode and a cathode, and one or more organic layers interposed between the anode and the cathode, at least one of the organic layers comprising the aromatic derivative according to claim 1.
3. An organic electroluminescent device according to claim 2, wherein: the organic layer comprises a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer which are sequentially arranged from the anode to the cathode; the cathode is provided with a covering layer.
4. An organic electroluminescent device according to claim 3, wherein: the hole transport layer contains the aromatic derivative.
5. An organic electroluminescent device according to claim 3, wherein: 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 positioned on the second hole transport layer.
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