CN112552291B - Organic electroluminescent material and organic electroluminescent device thereof - Google Patents

Organic electroluminescent material and organic electroluminescent device thereof Download PDF

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CN112552291B
CN112552291B CN202011479192.0A CN202011479192A CN112552291B CN 112552291 B CN112552291 B CN 112552291B CN 202011479192 A CN202011479192 A CN 202011479192A CN 112552291 B CN112552291 B CN 112552291B
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organic electroluminescent
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CN112552291A (en
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程晓光
王乐
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Hebei Ruixin Electronic Materials Co ltd
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Abstract

The invention discloses an organic electroluminescent material and an organic electroluminescent device thereof, which have the structure shown in the following formula. The compound has good thermal stability and high triplet state energy level, can balance the transfer of holes and electrons, has more sufficient energy transfer, and can effectively improve the efficiency and the service life of devices. By adopting the organic electroluminescent material as a blue host or blue doping, an organic electroluminescent device with high efficiency, high resolution, high brightness and long service life can be obtained.
Figure DDA0002835145340000011

Description

Organic electroluminescent material and organic electroluminescent device thereof
Technical Field
The invention belongs to the field of luminescent materials, and particularly relates to an organic electroluminescent material and an organic electroluminescent device thereof.
Background
The organic electroluminescent device (OLED) has the advantages of wide visual angle, high response speed, high definition, high resolution, flexible luminescence, low power consumption, small influence of environmental pressure and temperature and the like, and has wide application prospect. The OLED device is generally a sandwich-like structure, and includes positive and negative electrode film layers and an organic functional material layer sandwiched between the electrode film layers. And applying voltage to the electrodes of the OLED device, injecting positive charges from the positive electrode and injecting negative charges from the negative electrode, and transferring the positive charges and the negative charges in the organic layer under the action of an electric field to meet for composite luminescence. The display technology is expanded by the application fields of large-size display products such as smart phones, tablet computers, wearable electronics and televisions, and is a novel display technology with fast development and high technical requirements.
An efficient and long-lived organic electroluminescent device is generally the result of an optimized match of the device structure with various organic materials. Common OLED devices typically comprise the following classes of organic materials: hole injection materials, hole transport materials, electron transport materials, and light emitting materials (dyes or doped guest materials) and corresponding host materials of each color. However, the existing organic electroluminescent material has low stability and high efficiency roll-off under high brightness, thus preventing the wide application of the organic electroluminescent material.
Disclosure of Invention
In order to solve the technical problems, the invention provides an organic electroluminescent material and an organic electroluminescent device thereof.
An organic electroluminescent material has a general structural formula shown as formula I:
Figure BDA0002835145320000021
wherein Ar is 1 To Ar 4 Independently selected from substituted or unsubstituted C 6 -C 50 Aryl or heteroaryl of (a).
Furthermore, the heteroaryl contains one or more than two heteroatoms selected from N, O, S and Si.
Further, the structural formula of the organic electroluminescent material is selected from B 1 -B 15 Any one of:
Figure BDA0002835145320000022
Figure BDA0002835145320000031
further, having B 1 -B 15 Structures and derivatives and analogs derived from said structures, including novel structural compounds derived from said structures as structural precursors or as structural fragments.
The invention also provides an organic electroluminescent device which comprises a cathode layer, an anode layer and an organic layer which are sequentially laminated on the bottom plate, wherein the organic layer contains the organic electroluminescent material.
Further, the organic layer includes one or more than two layers of a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron injection layer, and an electron transport layer.
Furthermore, the layer of the organic electroluminescent material is one or more than two layers of a hole injection layer, a hole transport layer, a luminescent layer, a hole blocking layer, an electron injection layer and an electron transport layer.
Further, the above organic electroluminescent material may be used alone or in combination with other compounds.
In the present invention, the organic electroluminescent device is an anode which can be formed by depositing metal or an oxide having conductivity and an alloy thereof on a substrate by a sputtering method, electron beam evaporation, vacuum deposition or the like; and sequentially evaporating a hole injection layer, a hole transport layer, a luminescent layer, an air barrier layer and an electron transport layer on the surface of the prepared anode, and then evaporating a cathode.
In the present invention, the light emitting layer may be a red, yellow or blue light emitting layer. In the present invention, when the light-emitting layer is a blue light-emitting layer, the organic electroluminescent material is used as a blue host or blue dopant, so that an organic electroluminescent device with high efficiency, high resolution, high brightness and long lifetime can be obtained.
The organic electroluminescent material provided by the invention has better thermal stability and higher triplet state energy level, can balance the transfer of holes and electrons, has more sufficient energy transfer, and can effectively improve the efficiency and the service life of a device.
Drawings
Fig. 1 is a schematic structural diagram of an organic electroluminescent device according to the present invention.
Wherein, 1, a substrate; 2. an anode; 3. a hole injection layer; 4. a hole transport layer; 5. a light emitting layer; 6. a hole blocking layer; 7. an electron transport layer; 8. an electron injection layer; 9. and a cathode.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
Synthesis of Compounds 1-h
Figure BDA0002835145320000051
The first step is as follows: synthesis of intermediate 1-a
Methyl 2-bromo-5-chlorobenzoate (24.9g, 100mmol), 2-methoxy-2-naphthaleneboronic acid (20.2, 100 mmol), tetrakis (triphenylphosphine) palladium (3.4g, 0.29mmol), and potassium carbonate (30.2g, 217.2mmol) were put into a 500-mL round-bottomed flask, and 300mL of toluene, 100mL of ethanol, and 100mL of water were put into the flask. The temperature of the reactor was raised to 80 ℃ under nitrogen and stirred for 10 hours, after the reaction was completed, the temperature of the reactor was lowered to room temperature, and several layers were extracted and separated with toluene. The organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain intermediate 1-a (26.1 g, yield, 80%).
The second step: synthesis of intermediate 1-b
Adding 300mL of THF into a 500mL round-bottom flask reaction bottle, cooling the intermediate 1-a (26.1g, 79.9 mmol) to-40 ℃ with stirring, dropwise adding methyllithium (180.2mmol, 50ml) by using a balanced dropping funnel, keeping the temperature and stirring for 6 hours, heating the temperature to room temperature with stirring, stirring for 4 hours, adding hydrochloric acid dropwise into the solution after the reaction is finished, acidifying, demixing, carrying out rotary evaporation on an organic phase, and then adding n-hexane and ethyl acetate =10:1 was eluted and separated by silica gel column chromatography to obtain intermediate 1-b (18.3 g, yield, 70%).
The third step: synthesis of intermediate 1-c
A500 mL round-bottom flask was charged with 100mL of acetic acid, intermediate 1-b (18.3 g, 56mmol), and p-toluenesulfonic acid (1.0 g), and heated to reflux for 3 hours. After confirming the reaction through thin layer chromatography, the reaction was cooled to room temperature, precipitated, and the solid was filtered and washed with ethanol to obtain intermediate 1-c (12.1 g, yield, 70%).
The fourth step: synthesis of intermediate 1-d
Into a 500mL round bottom flask were charged 200mL of methylene chloride, intermediate 1-c (12.1g, 39.2mmol), boron tribromide: (10.0 g, 39.2mmol), stirring at 0 ℃ and stirring at the same temperature for 1 hour, transferring the reaction solution to 50mL of water, transferring the reaction solution to a separatory funnel, and extracting the mixture with dichloromethane. Then, the organic layer was dried over sodium sulfate, filtered, and concentrated. The residue was purified with methanol to give intermediate 1-d as a white solid (9.2 g, yield 80%).
The fifth step: synthesis of intermediates 1-e
Into a 500mL round bottom flask, 200mL of methylene chloride, intermediate 1-d (9.2g, 31.2mmol) and triethylamine (3.16g, 31.2mmol) were charged, and after completion of the reaction at 15 ℃ and dropwise addition of trifluoromethanesulfonic anhydride (4.7g, 31.3mmol), 100mL of water was added to the reaction vessel under stirring and the layers were separated. The organic phase was dried to dryness, filtered, concentrated, and the solid was recrystallized from petroleum ether to obtain intermediate 1-e (12.0 g, yield, 90%).
And a sixth step: synthesis of intermediate 1-f
A500 mL round-bottomed flask was charged with intermediate 1-e (12.0 g, 28.1mmol), 2-bromoboric acid (5.64g, 28.1mmol), tetrakis (triphenylphosphine) palladium (1.5g, 0.13mmol), and potassium carbonate (7.9g, 57mmol), and charged with 200mL of toluene, 50mL of ethanol, and 30mL of water. The temperature of the reactor was raised to 80 ℃ under nitrogen with stirring and stirred for 6 hours, after completion of the reaction, the temperature of the reactor was lowered to room temperature, and several layers were extracted and separated with toluene. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain intermediate 1-f (10.4 g, yield, 85%)
The seventh step: synthesis of intermediates 1-g
A250 mL round-bottom flask was charged with intermediate 1-f (10.4g, 23.9mmol), cesium carbonate (31.0g, 95.1mol), palladium acetate (1.35g, 0.6mmol), tri-tert-butylphosphine (0.14g, 0.8mmol), and 100mL of toluene, and stirred under reflux for 2 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and concentrated under reduced pressure. The substance was isolated and purified by column chromatography, and then recrystallized from isopropanol to obtain 1-g (6.6 g, 78%) of an intermediate.
Eighth step: synthesis of intermediates 1-h
A250 mL round-bottom flask was charged with 1-g of intermediate (6.6 g,18.7 mmol), potassium acetate (31.0 g,95.1 mol), pdCl2 (dppf) (0.68g, 0.93mmol), and 100mL of DMF, and stirred at reflux for 5 hours. After the reaction is finished, the reaction product is cooled at normal temperature. 200mL of water was added to precipitate a product, which was filtered and then recrystallized from ethanol to obtain a compound (1-h, 6.6g, 80%).
Example 2
Synthesis of Compound 2-c
Figure BDA0002835145320000081
The first step is as follows: synthesis of intermediate 2-a
1-bromo-2-fluoro-3-iodo-4-chlorobenzene (33.5g, 100mmol), 2-methoxy-3-boronic acid biphenyl (22.8g, 100mol), tetrakis (triphenylphosphine) palladium (3.4g, 0.29mmol), and potassium carbonate (30.2g, 217.2mmol) were charged in a 500mL round-bottomed flask, and 300mL of toluene, 100mL of ethanol, and 100mL of water were charged. The temperature of the reactor was raised to 80 ℃ under nitrogen and stirred for 10 hours, after the reaction was completed, the temperature of the reactor was lowered to room temperature, and several layers were extracted and separated with toluene. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain intermediate 2-a (33.2 g, yield, 85%).
The second step is that: synthesis of intermediate 2-b
Into a 500mL round bottom flask were charged 300mL of 2-a (33.2g 84.8 mmol) in methylene chloride, boron tribromide: (21.6 g, 39.2mmol), stirring at 0 ℃ and stirring at the same temperature for 1 hour, transferring the reaction solution to 100mL of water, adding the mixture to a separatory funnel, and extracting with dichloromethane. Then, the organic layer was dried over sodium sulfate, filtered, and concentrated. The residue was purified with methanol to give intermediate 2-b as a white solid (25.6 g, yield 80%).
The third step: synthesis of intermediate 2-c
To a 500mL round-bottom flask were added 2-b (25.6 g 71mmol), cesium carbonate (31.0 g,95.1 mol), palladium acetate (1.35g, 0.6 mmol), and NMP 200mL, and the mixture was stirred under reflux for 2 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. The substance was isolated and purified by column chromatography, and then recrystallized from isopropanol to obtain compound 2-c (21.0 g, 82%).
Example 3
Synthesis of Compound 3-b
Figure BDA0002835145320000091
A500-mL round-bottom flask was charged with 2-c (21.0g, 58.7mmol), 1-h (26.1, 58.7 mmol), tetrakis (triphenylphosphine) palladium (1.5g, 0.13mmol), and potassium carbonate (15.1g, 108mmol), and further charged with 250mL of toluene, 80mL of ethanol, and 50mL of water. The temperature of the reactor was raised to 80 ℃ under nitrogen and stirred for 10 hours, after completion of the reaction, the temperature of the reactor was lowered to room temperature and several layers were extracted and separated with toluene. The organic layer was concentrated under reduced pressure and then separated by column chromatography, thereby obtaining compound 3-b (26.2 g, yield, 75%).
Example 4
1) Compound A 1 Synthesizing:
Figure BDA0002835145320000092
a500 mL round-bottomed flask was charged with 2-amino-9, 9-dimethylfluorene (41.8g 200mmol), 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (38.8g100mmol), sodium t-butoxide (38.4 g, 400mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-t-butylphosphor (1.71g, 10mmol), and 300mL of toluene, and stirred at reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound A 1 (36.1g，70％)。
2) Compound A 2 The synthesis of (2):
Figure BDA0002835145320000101
adding into a 500mL round-bottom flask
Figure BDA0002835145320000102
(200mmol)、
Figure BDA0002835145320000103
(100 mmol), sodium tert-butoxide (38.4 g, 400mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), toluene (300 mL), and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound A 2 。
3) Compound A 3 Synthesis of (2)
Figure BDA0002835145320000111
In a 500mL round-bottom flask is added
Figure BDA0002835145320000112
(200mmol)、
Figure BDA0002835145320000113
(100 mmol), sodium tert-butoxide (38.4 g, 400mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10mmol), toluene 300mL, and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound A 3 。
4) Compound A 4 Synthesis of (2)
Figure BDA0002835145320000114
Adding into a 500mL round-bottom flask
Figure BDA0002835145320000121
(200mmol)、
Figure BDA0002835145320000122
(100 mmol), sodium tert-butoxide (38.4 g, 400mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), toluene (300 mL), and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound A 3 。
5) Compound A 5 Synthesis of (2)
Figure BDA0002835145320000123
Adding into a 500mL round-bottom flask
Figure BDA0002835145320000124
(200mmol)、
Figure BDA0002835145320000125
(100 mmol), sodium tert-butoxide (38.4 g, 400mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), toluene (300 mL), and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound A 5 。
6) Compound A 6 Synthesis of (2)
Figure BDA0002835145320000131
In a 500mL round-bottom flask is added
Figure BDA0002835145320000132
(200mmol)、
Figure BDA0002835145320000133
(100 mmol), sodium tert-butoxide (38.4 g, 400mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10mmol), toluene 300mL, and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound A 6 。
7) Compound A 7 Synthesis of (2)
Figure BDA0002835145320000134
In a 500mL round-bottom flask is added
Figure BDA0002835145320000135
(200mmol)、
Figure BDA0002835145320000136
(100 mmol), sodium tert-butoxide (38.4 g, 400mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), toluene (300 mL), and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound A 7 。
8) Compound A 8 Synthesis of (2)
Figure BDA0002835145320000141
In a 500mL round-bottom flask is added
Figure BDA0002835145320000142
(200mmol)、
Figure BDA0002835145320000143
(100 mmol), sodium tert-butoxide (38.4 g, 400mmol), pdCl2 (dppf) (0.68g, 0.93mmol),tri-tert-butylphosphine (1.71g, 10mmol), toluene (300 mL), and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound A 8 。
9) Compound A 9 Synthesis of (2)
Figure BDA0002835145320000144
In a 500mL round-bottom flask is added
Figure BDA0002835145320000151
(200mmol)、
Figure BDA0002835145320000152
(100 mmol), sodium tert-butoxide (38.4 g, 400mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), toluene (300 mL), and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound A 9 。
10 Compound A 10 Synthesis of (2)
Figure BDA0002835145320000153
Adding into a 500mL round-bottom flask
Figure BDA0002835145320000154
(200mmol)、
Figure BDA0002835145320000155
(100 mmol), sodium tert-butoxide (38.4 g, 400mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), toluene (300 mL), and stirred under reflux for 4 hours. After the reaction is finishedAnd (5) cooling at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound A 10 。
11 Compound A 11 Synthesis of (2)
Figure BDA0002835145320000161
In a 500mL round-bottom flask is added
Figure BDA0002835145320000162
(200mmol)、
Figure BDA0002835145320000163
(100 mmol), sodium tert-butoxide (38.4 g, 400mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), toluene 300mL, and stirring under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound A 11 。
12 Compound A 12 Synthesis of (2)
Figure BDA0002835145320000164
In a 500mL round-bottom flask is added
Figure BDA0002835145320000171
(200mmol)、
Figure BDA0002835145320000172
(100 mmol), sodium tert-butoxide (38.4 g, 400mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), toluene (300 mL), and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and concentrated under reduced pressureAnd (4) shrinking. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound A 12 。
13 Compound A) 13 Synthesis of (2)
Figure BDA0002835145320000173
In a 500mL round-bottom flask is added
Figure BDA0002835145320000174
(200mmol)、
Figure BDA0002835145320000175
(100 mmol), sodium tert-butoxide (38.4 g, 400mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10mmol), toluene 300mL, and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound A 13 。
14 Compound A) 14 Synthesis of (2)
Figure BDA0002835145320000181
In a 500mL round-bottom flask is added
Figure BDA0002835145320000182
(200mmol)、
Figure BDA0002835145320000183
(100 mmol), sodium tert-butoxide (38.4 g, 400mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), toluene (300 mL), and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanolTo obtain a compound A 14 。
Example 5
Compound B 1 Synthesis of (2)
Figure BDA0002835145320000191
A500 mL round-bottom flask was charged with 3-b (15.0 g, 25.2mmol) and A 1 (13.0g, 25.2mmol), sodium tert-butoxide (7.2g, 75.0mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g10mmol), toluene (200 mL), and stirred at reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound B 1 (19.5gg，72％)。
Example 6
Compound B 2 Synthesis of (2)
Figure BDA0002835145320000192
A500 mL round-bottomed flask was charged with 3-b (25.2 mmol), A 2 (25.2 mmol), sodium tert-butoxide (7.2g, 75.0 mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), and toluene (200 mL), and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound B 2 。
Example 7
Compound B 3 Synthesis of (2)
Figure BDA0002835145320000201
A500 mL round-bottom flask was charged with 3-b (25.2 mmol) and A 3 (25.2 mmol), sodium tert-butoxide (7.2 mmol)g,75.0 mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10mmol), and toluene (200 mL), and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound B 3 。
Example 8
Compound B 4 Synthesis of (2)
Figure BDA0002835145320000202
A500 mL round-bottomed flask was charged with 3-b (25.2 mmol), A 4 (25.2 mmol), sodium tert-butoxide (7.2g, 75.0 mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), and toluene (200 mL), and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound B 4 。
Example 9
Compound B 5 Synthesis of (2)
Figure BDA0002835145320000211
A500 mL round-bottomed flask was charged with 3-b (25.2 mmol), A 5 (25.2 mmol), sodium tert-butoxide (7.2g, 75.0 mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), and toluene (200 mL), and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound B 5 。
Example 10
Compound B 6 Synthesis of (2)
Figure BDA0002835145320000221
A500 mL round-bottom flask was charged with 3-b (15.0 g, 25.2mmol) and A 6 (25.2 mmol), sodium tert-butoxide (7.2g, 75.0 mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), and toluene 200mL, and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound B 6 。
Example 11
Compound B 7 Synthesis of (2)
Figure BDA0002835145320000222
A500 mL round-bottom flask was charged with 3-b (25.2 mmol) and A 7 (25.2 mmol), sodium tert-butoxide (7.2g, 75.0 mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), and toluene (200 mL), and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound B 7 。
Example 12
Compound B 8 Synthesis of (2)
Figure BDA0002835145320000231
A500 mL round-bottom flask was charged with 3-b (25.2 mmol) and A 1 (25.2 mmol), sodium tert-butoxide (7.2g, 75.0 mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), and toluene (200 mL), and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water and washed with magnesium sulfateDried and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound B 8 。
Example 13
Compound B 9 Synthesis of (2)
Figure BDA0002835145320000232
A500 mL round-bottom flask was charged with 3-b (25.2 mmol) and A 14 (25.2 mmol), sodium tert-butoxide (7.2g, 75.0 mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), and toluene 200mL, and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound B 9 。
Example 14
Compound B 10 Synthesis of (2)
Figure BDA0002835145320000241
A500 mL round-bottom flask was charged with 3-b (25.2 mmol) and A 8 (25.2 mmol), sodium tert-butoxide (7.2g, 75.0 mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), and toluene (200 mL), and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound B 10 。
Example 15
Compound B 11 Synthesis of (2)
Figure BDA0002835145320000251
A500 mL round-bottom flask was charged with 3-b (25.2 mmol) and A 9 (25.2 mmol), sodium tert-butoxide (7.2g, 75.0 mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), and toluene (200 mL), and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound B 11 。
Example 16
Compound B 12 Synthesis of (2)
Figure BDA0002835145320000252
A500 mL round-bottom flask was charged with 3-b (25.2 mmol) and A 10 (25.2 mmol), sodium tert-butoxide (7.2g, 75.0 mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), and toluene (200 mL), and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound B 12 。
Example 17
Compound B 13 Synthesis of (2)
Figure BDA0002835145320000261
A500 mL round-bottom flask was charged with 3-b (25.2 mmol) and A 11 (25.2 mmol), sodium tert-butoxide (7.2g, 75.0 mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), and toluene (200 mL), and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound B 13 。
Example 18
Compound B 14 Synthesis of (2)
Figure BDA0002835145320000262
A500 mL round-bottomed flask was charged with 3-b (25.2 mmol), A 12 (25.2 mmol), sodium tert-butoxide (7.2g, 75.0 mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), and toluene 200mL, and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound B 14 。
Example 19
Compound B 15 Synthesis of (2)
Figure BDA0002835145320000271
A500 mL round-bottom flask was charged with 3-b (25.2 mmol) and A 13 (25.2 mmol), sodium tert-butoxide (7.2g, 75.0 mmol), pdCl2 (dppf) (0.68g, 0.93mmol), tri-tert-butylphosphine (1.71g, 10 mmol), and toluene (200 mL), and stirred under reflux for 4 hours. After the reaction is finished, the reaction product is cooled at normal temperature. The organic layer was separated by adding 100mL of water, dried over magnesium sulfate, and then concentrated under reduced pressure. Separating and purifying the substance by column chromatography, and recrystallizing with isopropanol to obtain compound B 15 。
Application examples 1 to 5 and comparative examples 1 to 2
Coating thickness of Fisher company of
Figure BDA0002835145320000272
The ITO glass substrate is put in distilled water for cleaning for 2 times, ultrasonically cleaned for 30 minutes, repeatedly cleaned for 2 times by distilled water, ultrasonically cleaned for 10 minutes, and after the cleaning of the distilled water is finished, ultrasonically cleaned by THF, ethanol, acetone and methanol in sequence, dried, and then the dried substrate is put in a vacuum chamber for dryingThe substrate was transferred to a plasma cleaning machine, washed for 10 minutes, and then transferred to a deposition machine.
Then, a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron injection layer, an electron transport layer, and a cathode are sequentially vapor-deposited on the ITO.
Hole injection layer: 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-Hexaazatriphenylene (HATCN) having a thickness of 10nm;
the material of the hole transport layer is N, N '-diphenyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) with the thickness of 30nm;
a light emitting layer: as shown in Table 1, the thickness of the light-emitting layer was 15nm; the guest material is 3, 3-dicarbazole biphenyl, and the doping amount is 2wt%;
the material of the hole blocking layer is 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBi) with the thickness of 8nm;
the material of the electron injection layer is 8-hydroxyquinoline lithium (Liq), and the thickness is;
the material of the electron transport layer is lithium azide (LiN) 3 ) The thickness is 50nm;
the cathode is made of aluminum and has a thickness of 80nm.
Wherein the luminescent materials employed in comparative examples 1-2 were RD
Figure BDA0002835145320000281
TABLE 1 selection of materials for the light-emitting layer
Device with a metal layer Luminescent layer body Light-emitting object
Application example 1 Example 5 Is free of
Application example 2 Example 8 3, 3-dicarbazolbiphenyl
Application example 3 Example 10 3, 3-dicarbazolyl biphenyl
Application example 4 Example 14 3, 3-dicarbazolbiphenyl
Application example 5 Example 18 3, 3-dicarbazolbiphenyl
Comparative example 1 RD Is free of
Comparative example 2 RD 3, 3-dicarbazolyl biphenyl
Performance testing
The driving voltage and current efficiency of the organic electroluminescent devices prepared in the examples and comparative examples were measured at the same brightness using a PhotoResearch model PR750 type luminometer ST-86LA and a Keithley4200 test system. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent device reached 1000cd/m 2 Voltage at time, i.e. drive voltage, whileMeasuring the current density at the moment; the ratio of the luminance to the current density is the current efficiency.
Life test of LT95 is as follows: using a luminance meter at 1500cd/m 2 The luminance drop of the organic electroluminescent device was measured to 1425cd/m by maintaining a constant current at luminance 2 Time in hours
Table 1 shows the results of the performance tests of application examples 1 to 5 and comparative examples 1 to 2
Figure BDA0002835145320000291
According to the experimental data, the device prepared from the organic electroluminescent material has the advantages of lower driving voltage, higher current efficiency and longer service life; the organic electroluminescent material can effectively reduce the rise-fall voltage, improve the current efficiency and prolong the service life of the device, and is a main material with good performance.
In conclusion, the above embodiments are merely intended to illustrate the technical solution of the present invention and not to limit, although the present invention has been described by referring to certain preferred embodiments thereof, it should be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.

Claims (5)

1. An organic electroluminescent material, characterized in that the structure of the organic electroluminescent material is any one of B1, B4, B6, B10, B14:
Figure FDA0003813985710000011
2. an organic electroluminescent device comprising a cathode layer, an anode layer and an organic layer laminated in this order on a substrate, wherein the organic layer contains the organic electroluminescent material according to claim 1.
3. The organic electroluminescent device according to claim 2, wherein the organic layer comprises one or more layers selected from a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron injection layer, and an electron transport layer.
4. The organic electroluminescent device according to claim 3, wherein the layer containing the organic electroluminescent material according to claim 1 is one or more than two layers selected from a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron injection layer, and an electron transport layer.
5. The organic electroluminescent device as claimed in claim 2, wherein the organic electroluminescent material as claimed in claim 1 can be used alone or in combination with other compounds.
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