CN111763205B - Organic electroluminescent compound, preparation method thereof and organic electroluminescent device - Google Patents
Organic electroluminescent compound, preparation method thereof and organic electroluminescent device Download PDFInfo
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Abstract
The invention relates to the technical field of organic light-emitting materials, in particular to an organic electroluminescent compound, a preparation method thereof and an organic electroluminescent device, wherein the compound has the following structural formula:
Description
Technical Field
The invention relates to the technical field of organic light-emitting materials, in particular to an organic electroluminescent compound, a preparation method thereof and an organic electroluminescent device.
Background
An Organic Light-Emitting Diode (OLED) is also called an Organic electroluminescent display or an Organic Light-Emitting semiconductor. Was found in the laboratory in 1979 by professor Deng Qingyun of american chinese (Ching w.tang). The OLED display technology has the advantages of self-luminescence, wide viewing angle, almost infinite contrast, low power consumption, extremely high reaction speed and the like. However, the price of the high-end display screen is more expensive than that of the liquid crystal television.
The OLED display technology has a self-luminous characteristic, and uses a very thin organic material coating layer and a glass substrate, when a current flows, the organic material emits light, and the OLED display screen has a large viewing angle, and can save electric energy, and the display device is applied to an MP3 player since 2003. From then on, the method gradually enters the visual field of people and becomes a hot point of research.
However, the synthesis process of the conventional organic electroluminescent compound is complex, takes a long time, has a short lifetime, and therefore, in order to meet the current industrial application requirements of the OLED device and the photoelectric property requirements of the OLED device, a more suitable electroluminescent material with high performance must be selected to achieve the comprehensive properties of high efficiency, long lifetime, and low voltage of the device, and therefore, further development of the organic electroluminescent compound is urgent.
Disclosure of Invention
The present invention has been made to overcome the disadvantages of the prior art, and an object of the present invention is to provide an organic electroluminescent compound, a method of preparing the same, and an organic electroluminescent device, wherein the compound has good thermal stability, a simple preparation route, and an organic electroluminescent device containing the same has excellent luminous efficiency and long lifetime, is an organic electroluminescent compound having excellent properties, and is more simple, mature, and repeatable in preparation.
The technical scheme adopted by the invention is as follows:
an organic electroluminescent compound represented by the following general formula I:
wherein
Ar 1 、Ar 2 Each independently represents substituted or unsubstituted (C) 1 -C 30 ) Alkyl, (C) 2 -C 30 ) Alkenyl, (C) 2 -C 30 ) Alkynyl, substituted or unsubstituted (C) 3 -C 30 ) Cycloalkyl, substituted or unsubstituted (C) 3 -C 30 ) HeterocycloalkanesRadical, substituted or unsubstituted (C) 6 -C 30) Aryl or substituted or unsubstituted (3-to 30-membered) heteroaryl; substituted or unsubstituted (3-to 30-membered) heteroarylamino, substituted or unsubstituted C 6 ～C 60 Arylamine, (C) 1 -C 30 ) Alkoxy group, (C) 6 -C 60 ) An aryloxy group; or are linked to an adjacent substituent to form a monocyclic or polycyclic (C) 3 -C 30 ) An aliphatic or (3-to 30-membered) aromatic ring whose carbon atom may be replaced by at least one heteroatom selected from nitrogen, oxygen and sulfur;
R 1 、R 2 、R 3 the same or different from each other, and each independently is hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino, sulfonic acid, sulfonyl, phosphoric acid, phosphoryl, silicon, boryl; (C) 1 -C 30 ) Alkyl, (C) 2 -C 30 ) Alkenyl, (C) 2 -C 30 ) Alkynyl, substituted or unsubstituted (C) 3 -C 30 ) Cycloalkyl, substituted or unsubstituted (C) 3 -C 30 ) Heterocycloalkyl, substituted or unsubstituted (C) 6 -C 30 ) Aryl or substituted or unsubstituted (3-to 30-membered) heteroaryl; substituted or unsubstituted (3-to 30-membered) heteroarylamino, substituted or unsubstituted C 6 ～C 60 Arylamine, (C) 1 -C 30 ) Alkoxy group, (C) 6 -C 60 ) An aryloxy group; or are linked to an adjacent substituent to form a monocyclic or polycyclic (C) 3 -C 30 ) An aliphatic or (3-to 30-membered) aromatic ring, the carbon atom of which may be replaced by at least one heteroatom selected from nitrogen, oxygen and sulfur;
R 4 、R 5 independently is (C) substituted or unsubstituted 1 -C 30 ) Alkyl, substituted or unsubstituted (C) 1 -C 30 ) Alkoxy, substituted or unsubstituted (C) 3 -C 30 ) Cycloalkyl, substituted or unsubstituted (3-to 30-membered) heterocycloalkyl, substituted or unsubstituted (C) 6 -C 30 ) Aryl, substituted or unsubstituted (3-to 30-membered) heteroaryl, substituted or unsubstituted (C) 6 -C 30 ) Aryloxy, substituted or unsubstituted (C) 6 -C 30 ) An arylamine group; or are linked to an adjacent substituent to form a monocyclic or polycyclic (C) 3 -C 30 ) Aliphatic rings or substituted or unsubstituted (3-to 30-membered) aromatic rings, in which the carbon atoms may be replaced with one or more heteroatoms, such as nitrogen, oxygen, sulfur, silicon, and the like. R 4 、R 5 Preferably benzene or naphthalene.
L is a connecting bond; or substituted or unsubstituted (C) 6 -C 30 ) An aryl group; substituted or unsubstituted (3-to 30-membered) heteroaryl. Preferably benzene.
The substituent of the substituted substituent in the substituted or unsubstituted substituent is selected from hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino, sulfonic group, sulfonyl, phosphoric group, phosphoryl, silicon base and borane group; substituted or unsubstituted (C) 1 -C 30 ) Hydrocarbons (alkyl, alkenyl, alkynyl), substituted or unsubstituted (C) 1 -C 30 ) Alkoxy, substituted or unsubstituted (C) 3 -C 30 ) Cycloalkyl, substituted or unsubstituted (C) 3 -C 30 ) Cycloalkenyl, substituted or unsubstituted (C) 3 -C 30 ) Heterocycloalkyl, substituted or unsubstituted (C) 6 -C 30 ) Aryl, substituted or unsubstituted (3-to 30-membered) heteroaryl, substituted or unsubstituted (C) 6 -C 30 ) Aryloxy, substituted or unsubstituted (C) 6 -C 30 ) An arylamine group; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted mono-or polycyclic ring (C) 3 -C 30 ) An aliphatic ring or a substituted or unsubstituted (3-to 30-membered) aromatic ring, the carbon atom of which may be replaced by at least one heteroatom selected from nitrogen, oxygen and sulfur.
In the above technical solution, the most preferred organic electroluminescent compound is selected from any one of the following structures:
a preparation method of an organic electroluminescent compound shown as a general formula I comprises the following synthetic route:
wherein R is 1 -R 5 、Ar 1 、Ar 2 And L is as defined above for formula I, hal1-Hal4 are halogen, which may be the same or different, and are preferably Cl, br.
1) And synthesis of an intermediate I-3: adding the reactant I-1 (1.0 eq), the reactant I-2 (1.1 eq), sodium tert-butoxide (2.0 eq) and a palladium catalyst (0.01 eq) into toluene, heating to 110 ℃ under the protection of nitrogen, and stirring for 12 hours. After the reaction is finished, washing with water at normal temperature, separating liquid, concentrating an organic phase, precipitating with petroleum ether, and filtering to obtain an intermediate I-3.
2) And synthesis of an intermediate I-4: adding the intermediate I-3 into triethyl phosphite, heating to 120 ℃, and stirring for 6h. After the reaction is finished, water is slowly added at normal temperature, solid is separated out by stirring, and the intermediate I-4 is obtained by filtering and drying.
3) And synthesis of an intermediate I-6: dissolving the intermediate I-4 (1.0 eq) in toluene, adding the reactant I-5 (1.1 eq), adding a palladium catalyst (0.01 eq), tri-tert-butylphosphine (1.0 eq) and sodium tert-butoxide (3.0 eq) under the protection of nitrogen, and heating to reflux and stirring for 12 hours. And after the reaction is finished, adding water for washing, separating liquid, concentrating the product solution, precipitating with petroleum ether, and filtering to obtain an intermediate I-6.
4) And synthesizing an intermediate I-8: dissolving the intermediate I-6 (1.0 eq) in toluene, adding the reactant I-7 (1.1 eq), adding a palladium catalyst (0.01 eq), tri-tert-butylphosphine (0.1 eq) and sodium tert-butoxide (3.0 eq) under the protection of nitrogen, and heating to reflux and stirring for 12 hours. After the reaction, water and dichloromethane were added at room temperature for extraction, the organic layer was concentrated and mixed with silica gel, and column chromatography (DCM: PE = 1:5) was carried out to obtain compound I-8.
5) Synthesis of the final product of general formula I: dissolving the intermediate I-8 (1.0 eq) in toluene, adding the reactant I-9 (1.1 eq), adding a palladium catalyst (0.01 eq), tri-tert-butylphosphine (0.1 eq) and sodium tert-butoxide (3.0 eq) under the protection of nitrogen, and heating to reflux and stirring for 12 hours. After the reaction is finished, water and dichloromethane are added for extraction at normal temperature, an organic layer is concentrated and mixed with silica gel, and column chromatography (DCM: PE = 1:7) is carried out to obtain the compound shown in the general formula I.
The compound has good thermal stability and simple preparation route, and an organic electroluminescent device containing the compound has excellent luminous efficiency and long service life and is an organic electroluminescent compound with excellent performance.
The specific implementation mode is as follows:
in order to further illustrate the present invention, the following will describe the organic light emitting compound provided by the present invention, the preparation method thereof and the organic electroluminescent device in detail with reference to the examples.
Example 1:
the reaction mixture 1-1 (50 mmol), the reaction mixture 1-2 (55 mmol), (100 mmol) sodium tert-butoxide and 1mmol dipalladium were added to 150ml toluene and stirred at 110 ℃ for 12 hours under nitrogen. After the reaction, the reaction mixture was washed with water at room temperature, separated, and the organic phase was concentrated, precipitated with petroleum ether, and filtered to obtain intermediate 1-3 (18.2 g, yield 80%, MW: 454.47).
The intermediates shown in Table 1 below can be synthesized according to the above-described method for synthesizing intermediates 1 to 3.
Table 1 example 1 summary of the reaction materials and product structures and characterization
Example 2:
40mmol of intermediate 1-3 are added to 160mL triethyl phosphite and stirred at 120 ℃ for 6h. After the reaction, water was slowly added at normal temperature, and the solid was precipitated by stirring, filtered and dried to obtain intermediate 1-4 (12.8 g, yield 76%, MW: 422.94).
The intermediates shown in the following Table 2 can be synthesized according to the method for synthesizing the intermediates 1 to 4, but not limited to the following intermediates.
Table 2 example 2 summary of reaction starting materials and product structures and characterization
Example 3:
dissolving the intermediate 1-4 (30 mmol) in toluene, adding the reactant 1-5 (33 mmol), adding Pd under the protection of nitrogen 2 (dba) 3 (0.3 mmol), tri-tert-butylphosphine (3 mmol), and sodium tert-butoxide (90 mmol), and the mixture was stirred under reflux for 12 hours. After the reaction, water washing was added at normal temperature, the product solution was separated and concentrated, precipitated with petroleum ether, and filtered to obtain intermediate 1-6 (13.3 g, yield: 77%, MW: 576.85).
Following the procedure for the synthesis of intermediates 1-6, the intermediates shown in Table 3 below can be synthesized.
Table 3 example 3 summary of reaction starting materials and product structures and characterization
Example 4:
dissolving the intermediate 1-6 (22 mmol) in toluene, adding the reactant 1-7 (24.2 mmol), adding Pd under the protection of nitrogen 2 (dba) 3 (0.22 mmol), tri-tert-butylphosphine (2.2 mmol), and sodium tert-butoxide (66 mmol), and the mixture was stirred under reflux for 12 hours. After the reaction, water and dichloromethane were added at room temperature to extract, the organic layer was concentrated and mixed with silica gel, and column chromatography (DCM: PE = 1:5) was carried out to obtain compounds 1 to 8 (5.36 g, yield: 75%, MW: 589.57).
The compounds shown in Table 4 below were synthesized according to the methods for the compounds 1 to 8.
Table 4 example 4 summary of reaction starting materials and product structures and characterization
Example 5:
the intermediate 1-8 (16 mmol) is dissolved in 150ml toluene, the reactant 1-9 (17.6 mmol) is added, and dipalladium (0.16 mmol), tri-tert-butylphosphine (1.6 mmol) and sodium tert-butoxide (48 mmol) are added under nitrogen protection, and the mixture is heated to reflux and stirred for 12 hours. After the reaction was completed, water and dichloromethane were added to extract at room temperature, the organic layer was concentrated and mixed with silica gel, and column chromatography (DCM: PE = 1:7) was carried out to obtain compound 1 (8.5 g, yield: 80%, MW: 665.52). The final products shown in Table 5 were prepared according to the above method.
Table 5 example 5 summary of reaction starting materials and product structures and characterization
The invention also provides an organic electroluminescent device which comprises the organic luminescent compound or the organic luminescent compound prepared by the preparation method.
The organic electroluminescent device may be any organic electroluminescent device known to those skilled in the art, and the present invention preferably includes a first electrode, a second electrode, and one or more organic layers disposed between the first electrode and the second electrode; at least one of the organic layers comprises the organic light-emitting compound described above.
In the present invention, the organic layer refers to all layers between the first electrode and the second electrode of the organic electroluminescent device. At least one of the organic layers is a light-emitting layer.
When the organic layer of the present invention includes a hole injection layer, a hole transport layer, and a layer having both hole injection and hole transport properties, it is preferable that at least one of the hole injection layer, the hole transport layer, and the layer having both hole injection and hole transport properties includes a hole injection material, a hole transport material, or a material having both hole injection and hole transport properties. When the organic layer is of a single-layer structure, the organic layer is a light-emitting layer, and when the organic layer is of a multilayer structure, the organic layer comprises a light-emitting layer; the light emitting layer preferably includes one or more of a phosphorescent host, a fluorescent host, a phosphorescent dopant material, and a fluorescent dopant material.
When the organic layer includes a hole transport layer, the hole transport layer includes an organic light emitting compound represented by formula I.
Compared with other hole transport layer materials, the organic luminescent compound provided by the invention has the advantages that the luminous efficiency is obviously improved, and the service life is obviously improved. The organic luminescent compound has the advantages of short synthetic route, simple process, easily obtained raw materials and low cost, and is suitable for industrial production.
Device example 1:
the ITO glass substrate with the coating thickness of 150nm is placed in distilled water for cleaning for 2 times, ultrasonic cleaning is carried out for 30 minutes, the ITO glass substrate is repeatedly cleaned for 2 times by the distilled water, the ultrasonic cleaning is carried out for 10 minutes, after the cleaning by the distilled water is finished, solvents such as isopropanol, acetone, methanol and the like are sequentially subjected to ultrasonic cleaning and then dried, the ITO glass substrate is transferred into a plasma cleaning machine, the ITO glass substrate is cleaned for 5 minutes, and the ITO glass substrate is sent into an evaporation machine. Evaporating 4,4', 4' -tri [ 2-naphthyl phenylamino ] group with the thickness of 50nm on the prepared ITO transparent electrode]Triphenylamine (2-TNATA) as a hole injection layer. Then, compound 1 was vacuum-evaporated on the formed hole injection layer to form a hole transport layer having a thickness of 50nmA layer. Then, a host material CBP and a phosphorescent dopant material Ir (bty) with a thickness of 40nm are vapor-deposited on the hole transport layer 2 (acac). The weight ratio of the host material to the dopant material was 95. Then, alq3 with a thickness of 60nm was vacuum-deposited on the light-emitting layer as an electron transporting layer. Lithium fluoride (LiF) was vacuum-deposited on the electron transport layer to a thickness of 0.5nm as an electron injection layer. Finally, aluminum with the thickness of 100nm is evaporated and used as a cathode, and therefore the preparation of the organic electroluminescent device is completed. And testing the performance luminescence characteristics of the obtained device.
By referring to the above-mentioned methods, the compound 1 in device example 1 was replaced with the compound 2,3,6,7, 33, 45, 52, 53, 54, 63 obtained in example 5, respectively, as a hole transport layer, to prepare the corresponding organic electroluminescent devices 2,3, 4, 5, 6,7, 8, 9, 10, 11.
Comparative example 1:
an organic electroluminescent device was produced in the same manner as in example 1, except that the compound NPB was used instead of the compound 1.
Applying forward DC bias voltage to the prepared organic electroluminescent device, measuring the organic electroluminescent characteristics, and controlling the voltage at 5000cd/m 2 The life of T95 was measured at the reference gray scale of (a). The results are shown in Table 6.
Table 6 device example 1 to device example 11 and comparative example 1 organic electroluminescent device test results
The luminance of the device test is 5000cd/m 2 From the results of Table 6, it can be seen that the compounds of the present invention can be appliedIn an OLED light emitting device, and in comparison to a comparative example, the voltage, efficiency and lifetime are improved over known OLED materials.
As can be seen from the results of table 6, the organic electroluminescent device prepared using the compound provided by the present invention as a hole transport layer has a significantly reduced driving voltage, and significantly improved luminous efficiency and lifetime, as compared to the organic electroluminescent device prepared using the compound NPB of comparative example as an electron transport layer.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (4)
1. An organic electroluminescent compound characterized by: the compounds are represented by the following general formula I:
wherein
Ar 1 、Ar 2 Each independently represents a substituted or unsubstituted C 6 -C 30 Aryl or substituted or unsubstituted 3 to 30 membered heteroaryl; substituted or unsubstituted 3-to 30-membered heteroarylamino, substituted or unsubstituted C 6 ～C 60 Arylamino, C 6 -C 60 An aryloxy group;
R 1 、R 2 、R 3 the same or different from each other, and each independently is hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino, sulfonic acid, sulfonyl, phosphoric acid, phosphoryl, silicon, boryl; c 1 -C 30 Alkyl radical, C 2 -C 30 Alkenyl radical, C 2 -C 30 Alkynyl, throughSubstituted or unsubstituted C 3 -C 30 Cycloalkyl, substituted or unsubstituted C 3 -C 30 Heterocycloalkyl, substituted or unsubstituted C 6 -C 30 Aryl or substituted or unsubstituted 3 to 30 membered heteroaryl; substituted or unsubstituted 3-to 30-membered heteroarylamino, substituted or unsubstituted C 6 ～C 60 Arylamino, C 1 -C 30 Alkoxy radical, C 6 -C 60 An aryloxy group;
R 4 、R 5 independently represents substituted or unsubstituted C 1 -C 30 Alkyl, substituted or unsubstituted C 1 -C 30 Alkoxy, substituted or unsubstituted C 3 -C 30 Cycloalkyl, substituted or unsubstituted 3-to 30-membered heterocycloalkyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, substituted or unsubstituted C 6 -C 30 Aryloxy, substituted or unsubstituted C 6 -C 30 An arylamine group;
l is substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted 3 to 30 membered heteroaryl;
the substituent of the substituted substituent in the substituted or unsubstituted substituent is selected from hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino, sulfonic group, sulfonyl, phosphoric group, phosphoryl, silicon base and borane group; unsubstituted C 1 -C 30 Hydrocarbons, unsubstituted C 1 -C 30 Alkoxy, unsubstituted C 3 -C 30 Cycloalkyl, unsubstituted C 3 -C 30 Cycloalkenyl, unsubstituted C 3 -C 30 Heterocycloalkyl, unsubstituted C 6 -C 30 Aryl, unsubstituted 3-to 30-membered heteroaryl, unsubstituted C 6 -C 30 Aryloxy, unsubstituted C 6 -C 30 An arylamine group.
2. An organic electroluminescent compound according to claim 1, wherein: the organic electroluminescent compound is selected from any one of the following structures:
3. a method for preparing the organic electroluminescent compound according to claim 1, which comprises the following steps:
Ar 1 、Ar 2 、R 1 -R 5 l is as defined in claim 1, hal 1 -Hal 4 Is halogen, identical or different;
the method comprises the following specific steps:
1) And synthesis of an intermediate I-3: 1.0eq of the reactant I-1, 1.1eq of the reactant I-2, 2.0eq of sodium tert-butoxide, 0.01eq of a palladium catalyst pd 2 (dba) 3 Adding into toluene, heating to 110 deg.C under nitrogen protection, stirring for 12 hr, reacting, washing with water at room temperature, separating, concentrating organic phase, separating with petroleum ether, and filtering to obtain intermediate I-3;
2) And synthesis of an intermediate I-4: adding the intermediate I-3 into triethyl phosphite, heating to 120 ℃, stirring for 6 hours, after the reaction is finished, slowly adding water at normal temperature, stirring to separate out a solid, filtering and drying to obtain an intermediate I-4;
3) And synthesis of an intermediate I-6: 1.0eq of intermediate I-4 was dissolved in toluene, 1.1eq of reactant I-5 was added, 0.01eq of palladium catalyst pd was added under nitrogen protection 2 (dba) 3 Heating 1.0eq of tri-tert-butylphosphine and 3.0eq of sodium tert-butoxide to reflux and stirring for 12 hours, adding water to wash at normal temperature after the reaction is finished, separating liquid and concentrating the product solution, precipitating with petroleum ether, and filtering to obtain an intermediate I-6;
4) And synthesis of an intermediate I-8: dissolving 1.0eq of intermediate I-6 in toluene, adding 1.1eq of reactant I-7, adding 0.01eq of palladium catalyst pd under the protection of nitrogen 2 (dba) 3 Heating to reflux and stirring for 12 hours, adding water and dichloromethane for extraction at normal temperature after the reaction is finished, concentrating an organic layer and mixing silica gel, and performing column chromatography on DCM, wherein PE =1:5 is used for obtaining a compound I-8;
5) Synthesis of the final product of general formula I: dissolving 1.0eq of intermediate I-8 in toluene, adding 1.1eq of I-9 into the reaction mixture, adding 0.01eq of palladium catalyst pd under the protection of nitrogen 2 (dba) 3 Heating to reflux and stirring for 12 hours, adding water and dichloromethane for extraction, concentrating an organic layer and mixing with silica gel at normal temperature after the reaction is finished, and carrying out column chromatography on DCM, wherein PE =1:7 is used for obtaining the compound shown in the general formula I.
4. An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.
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