CN110878088A - Compound and application thereof - Google Patents

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CN110878088A
CN110878088A CN201811036025.1A CN201811036025A CN110878088A CN 110878088 A CN110878088 A CN 110878088A CN 201811036025 A CN201811036025 A CN 201811036025A CN 110878088 A CN110878088 A CN 110878088A
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魏金贝
李国孟
高文正
代志宏
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Beijing Eternal Material Technology Co Ltd
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Abstract

The invention discloses a novel organic compound, which is shown as the following formula (1):
Figure DDA0001790634150000011
wherein: l is1And L2Each independently selected fromSingle bond, substituted or unsubstituted C6‑C30Aryl, substituted or unsubstituted C3‑C30One of the heteroaryl groups of (a); f1And F2Each independently selected from hydrogen and C1‑C12Alkyl, substituted or unsubstituted C6‑C30Aryl, substituted or unsubstituted C3‑C30One of the heteroaryl groups of (a); ar (Ar)1Selected from substituted or unsubstituted C6‑C30Aryl, substituted or unsubstituted C3‑C30The heteroaryl group of (a); ar (Ar)2Selected from substituted or unsubstituted C6‑C30Aryl, substituted or unsubstituted C3‑C30The heteroaryl group of (a); when L is1And L2In the same phase, Ar1And Ar2Are not identical. The compound of the invention shows excellent device performance and stability when being used as an electron transport material in an OLED device. The invention also protects the organic electroluminescent device adopting the compound with the general formula.

Description

Compound and application thereof
Technical Field
The invention relates to an imidazole-substituted chrysene organic compound which can be used as an electron transport material of an organic electroluminescent device; the invention also relates to the application of the compound in an organic electroluminescent device.
Background
The electroluminescent phenomenon based on organic small molecule materials is first reported in 1987 by professor of chinese scientist dunqing cloud, and organic electroluminescent diodes (OLEDs) have the advantages of self luminescence, high contrast, low power consumption and the like, so that the organic electroluminescent diodes attract extensive attention in the academic world and the industrial world. At present, the organic electroluminescent device structure in the display and lighting field is often composed of functional layers such as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
Electron transport materials with good electron transport and injection capabilities are still lacking. In addition, the higher exciton injection energy barrier often causes deviation of exciton recombination region under high voltage, and further causes phenomena of unstable electroluminescent spectrum, serious efficiency roll-off and the like. Therefore, the development of the electron transport material with good electron transport capability has important significance in the aspects of reducing the starting voltage, improving the luminous efficiency, reducing the efficiency roll-off and the like. As a common fused ring molecule, a chrysene material is often used in the light emitting layer as a blue or green dye. There is currently little report on flexor electron transport materials, especially asymmetric transport materials, and symmetric molecules based on the flexor nucleus are reported in patent TW200920718, but the driving voltage using the device still needs to be reduced.
Figure BDA0001790634140000011
The existing organic electroluminescent materials still have room for improvement in light-emitting performance, and development of new organic electroluminescent functional layer materials is urgently needed in the industry.
Disclosure of Invention
In order to solve the above-mentioned problems (i.e., weak electron transport ability and high injection energy barrier) in the prior art, the inventors have studied to introduce an imidazole unit into a bent skeleton, to improve the electron transport ability of the molecule, and to reduce the injection energy barrier of charges.
The invention provides a novel compound, the structure of which is shown as general formula (1):
Figure BDA0001790634140000021
in formula (1):
L1and L2Each independently selected from the group consisting of a single bond, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30One of the heteroaryl groups of (1), preferably, L1、L2Each independently selected from phenyl or pyridyl;
Ar1selected from substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30The heteroaryl group of (a);
and when L is1And L2In the same phase, Ar1And Ar2Different;
F1and F2Each independently selected from hydrogen and C1-C12Alkyl, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30One of the heteroaryl groups of (a);
Ar1more preferred are the following groups:
Figure BDA0001790634140000031
wherein, X1-X4C, CH or N, and of which up to 2 are N atoms;
a1 and A2 are each independently substituted or unsubstituted C6-C30With condensed ring aryl or substituted or unsubstituted C5-C30The fused ring heteroaryl of (a); r1And R3Each independently selected from: hydrogen, C1-C10Alkyl radical, C6-C15Aryl of (C)3-C15One of the heteroaryl groups of (a).
Ar1More preferred are the following groups:
Figure BDA0001790634140000041
wherein R is1And R3Each independently selected from: hydrogen, C1-C10Alkyl radical, C6-C15Aryl of (C)3-C15One of the heteroaryl groups of (a);
Ar1preferably selected from substituted or unsubstituted imidazole groups;
Ar2selected from substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30The heteroaryl group of (a);
Ar2preferred are acceptor groups as follows: a substituted or unsubstituted triazine group, a substituted or unsubstituted pyrimidine group, a substituted or unsubstituted pyridine group, a substituted or unsubstituted quinazoline group, a substituted or unsubstituted isoquinazoline group, a substituted or unsubstituted benzopyrazine group, a substituted or unsubstituted diphenylphosphine oxide group, a substituted or unsubstituted triphenylphosphine oxide group, or the like;
Ar2more preferred are the following groups:
Figure BDA0001790634140000042
wherein R is1-R3Each independently represents a single substituent up to the maximum permissible substituent orNo substituent group; and each is independently selected from the group consisting of: hydrogen, C1-C10Alkyl radical, C6-C15Aryl of (C)3-C15The heteroaryl group of (a).
Figure BDA0001790634140000053
Indicating the connection location.
When the above groups have substituents, the substituents are respectively and independently selected from halogen, cyano, C1-C10Alkyl or cycloalkyl of, C2-C6Alkenyl or cycloalkenyl of1-C6Alkoxy or thioalkoxy of C6-C30Monocyclic or condensed ring aryl of, C3-C30Or a fused ring heteroaryl, or a combination of these groups.
Further, the compound of the general formula of the present invention is preferably represented by the following formula (1-1) or formula (1-2):
Figure BDA0001790634140000051
in the formula (1-1) or the formula (1-2), L1And L2、F1And F2、Ar1And Ar2Are the same as defined in formula (1).
Further, the compound represented by the general formula (1) of the present invention can be represented by a specific compound M1-M116.
Figure BDA0001790634140000052
Figure BDA0001790634140000061
Figure BDA0001790634140000071
Figure BDA0001790634140000081
Figure BDA0001790634140000091
Figure BDA0001790634140000101
The invention also provides, as another aspect thereof, the use of a compound as described above in an organic electroluminescent device. The compounds of the invention are preferably used as electron transport materials in organic electroluminescent devices.
As still another aspect of the present invention, the present invention also provides an organic electroluminescent device comprising a first electrode, a second electrode and a plurality of organic layers interposed between the first electrode and the second electrode, characterized in that the organic layers contain an organic compound represented by the above general formula (1).
The specific reason why the above-mentioned compound of the present invention is excellent as an electron transporting material is not clear, and it is presumed that the following reasons may be mentioned:
the compound of the invention leads imidazole and other acceptor groups into the molecular skeleton, so that the electron transport capability of the molecule is enhanced, and when the material is used as the electron transport layer material of the organic electroluminescent device, compared with the prior art, the driving voltage can be further reduced, and the luminous efficiency can be improved.
The technical scheme of the invention has the following advantages:
(1) the chrysene group has good conjugation property and high carrier mobility, and is beneficial to the transmission of electrons.
(2) The imidazole groups have good electronic transmission capability, and can effectively reduce injection energy barrier and turn-on voltage when used as an electronic transmission material.
(3) Takes the chrysene as a central nucleus and imidazole and other receptor groups as substituents, can enrich the intra-molecular and intermolecular forces and improve the electron transport capacity.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments in order to make the present invention better understood by those skilled in the art.
Compounds of synthetic methods not mentioned in the present invention are all starting products obtained commercially. Solvents and reagents used in the present invention, such as methylene chloride, petroleum ether, ethanol, tetrahydrofuran, N-dimethylacetamide, anhydrous magnesium sulfate, carbazole, benzimidazole and the like, can be purchased from domestic chemical product markets, such as reagents from national drug group, TCI, shanghai Bidi medicine, carbofuran, and the like. In addition, they can be synthesized by a known method by those skilled in the art.
The analytical testing of intermediates and compounds in the present invention uses an abciex mass spectrometer (4000QTRAP) and a siemens analyzer.
The synthesis of the compounds of the present invention is briefly described below.
Synthesis example 1: synthesis of M1
Figure BDA0001790634140000111
Synthesis of intermediate M1-1:
31.4g (100mmol) of [4- (2-phenyl-1H-benzimidazol-1-yl) phenyl]Boric acid and 46.1g (120mmol) of 6, 12-dibromochrysin are introduced into a freshly baked 3000mL two-necked flask, 20.7g (150mmol) of anhydrous potassium carbonate, 2.31g (2mmol) of palladium tetratriphenylphosphine and 75mL of water and 1200mL of 1, 4-dioxane are added under nitrogen, and the reaction is then heated to reflux for 20 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and poured into 2L of ice water under stirring, whereupon a large amount of pale yellow precipitate was produced. Vacuum filtering, and repeatedly washing the filter cake with distilled water. Column chromatography with dichloromethane as eluent gave a pale yellow mixed solid which was sublimed in vacuo to give an off-white solid, 25.8g, 45% yield. The mass of the molecules determined by mass spectrometry was: 574.12 (calculated value: 574.10); theoretical element content (%) C37H23BrN2：C，77.22；H，4.03；Br，1388; and N, 4.87. Measured elemental content (%): c, 77.23; h, 4.08; and N, 4.85. The above analysis results show that the obtained product is the expected product.
Synthesis of intermediate M1-2:
a dry 1000mL three-necked flask is taken, 5.7g (10mmol) of the M1-1 intermediate obtained in the first step, 5.1g (20mmol) of pinacol diboron diboride and 1.46g (2mmol) of 1,1' -bis (diphenylphosphine) ferrocene palladium dichloride are sequentially added under the nitrogen condition, and finally 500mL of dry 1, 4-dioxane is added for reflux reaction for 15 h. After the completion of the reaction, the solvent in the reaction system was removed by distillation under reduced pressure. Extraction with dichloromethane, washing with a large amount of water, combining organic phases and performing column chromatography. Dichloromethane: column chromatography with petroleum ether 1:1 as eluent gave a large amount of white solid, 4.1g, 66% yield. The molecular masses determined by mass spectrometry were: 622.30 (calculated value: 622.28); theoretical element content (%) C43H35BN2O2: c, 82.96; h, 5.67; b, 1.74; n, 4.50; and O, 5.14. Measured elemental content (%): c, 82.90; h, 5.66; n, 4.52. The above analysis results show that the obtained product is the expected product.
Synthesis of compound M1:
a dry 500mL two-necked flask was taken and charged with 4.1g (6.6mmol) of M1-2, 2.67g (10mmol) of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, 1.38g (10mmol) of anhydrous potassium carbonate and 230mg (2mmol) of tetrakistriphenylphosphine palladium in that order. After nitrogen substitution was carried out three times, 5mL of water, 5mL of ethanol and 300mL of toluene were added, and the mixture was refluxed for 12 hours. The solvent of the reaction system was distilled under reduced pressure, extracted with dichloromethane, and washed with a large amount of water. After combining the organic phases, concentrate to yield a mixture of dichloromethane: column chromatography with petroleum ether 5:1 as eluent gave 3.2g of a white solid in 66% yield. The mass of the molecules determined by mass spectrometry was: 727.25 (calculated value: 727.27); theoretical element content (%) C52H33N5: c, 85.81; h, 4.57; and N, 9.62. Measured elemental content (%): c, 85.77; h, 4.57; and N, 9.61. The above analysis results show that the obtained product is the expected product.
Synthesis example 2: synthesis of M3:
according to the synthesis of M1, the procedure was the same, using 2-chloro-4, 6-diphenylpyrimidine instead of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine to react, 3.1g of white solid was obtained, yield 65%. The mass of the molecules determined by mass spectrometry was: 726.26 (calculated value: 726.28); theoretical element content (%) C53H34N4: c, 87.58; h, 4.71; and N, 7.71. Measured elemental content (%): c, 87.57; h, 4.72; and N, 7.69. The above analysis results show that the obtained product is the expected product.
Synthesis example 3: synthesis of M9:
following the synthesis of M1, the procedure was the same, substituting 2- (4-bromophenyl) -4, 6-diphenylpyrimidine for 2-chloro-4, 6-diphenyl-1, 3, 5-triazine to give 3.6g of a white solid in 65% yield. The mass of the molecules determined by mass spectrometry was: 803.28 (calculated value: 803.30); theoretical element content (%) C58H37N5: c, 86.65; h, 4.64; n, 8.71. Measured elemental content (%): c, 86.67; h, 4.62; and N, 8.69. The above analysis results show that the obtained product is the expected product.
The light-emitting layer of the organic electroluminescent device and the organic electroluminescent device of the present invention will be explained below.
The light-emitting layer of the organic electroluminescent device comprises a host material and a dye. The compound of the present invention can be used as a host material or an electron transport layer material.
The OLED includes first and second electrodes, and an organic material layer between the electrodes. The organic material may in turn be divided into a plurality of regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.
In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a Thin Film Transistor (TFT) may be provided on a substrate for a display.
The first electrode may be formed by sputtering or depositing a material used as the first electrode on the substrate. When the first electrode is used as an anode, an oxide transparent conductive material such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), or any combination thereof may be used. When the first electrode is used as a cathode, a metal or an alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof can be used.
The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, printing, or the like. The compound used as the organic material layer may be an organic small molecule, an organic large molecule, and a polymer, and a combination thereof.
The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer containing only one compound and a single layer containing a plurality of compounds. The hole transport region may also be a multilayer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL).
The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenevinylene, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives such as compounds shown below in HT-1 to HT-34; or any combination thereof.
Figure BDA0001790634140000131
Figure BDA0001790634140000141
Figure BDA0001790634140000151
The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of a plurality of compounds. For example, the hole injection layer may employ one or more compounds of HT-1 to HT-34 described above, or one or more compounds of HI1-HI3 described below; one or more of the compounds HT-1 to HT-34 may also be used to dope one or more of the compounds HI1-HI3 described below.
Figure BDA0001790634140000152
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The host material of the light emitting layer is selected from, but not limited to, one or more of GPH-1 to GPH-80.
Figure BDA0001790634140000153
Figure BDA0001790634140000161
Figure BDA0001790634140000171
Figure BDA0001790634140000181
In one aspect of the invention, the light-emitting layer employs a thermally activated delayed fluorescence emission technique. The fluorescent dopant of the light-emitting layer can be selected from, but is not limited to, one or more of TDE1-TDE39 listed below.
Figure BDA0001790634140000182
Figure BDA0001790634140000191
Phosphorescent dyes may be, but are not limited to, combinations of one or more of PD1-PD17 listed below.
Figure BDA0001790634140000201
An electron injection layer may also be included in the device between the electron transport layer and the cathode, the electron injection layer material including, but not limited to, combinations of one or more of the following:
LiQ,LiF,NaCl,CsF,Li2O,Cs2CO3,BaO,Na,Li,Ca。
the cathode is metal, metal mixture or oxide such as magnesium silver mixture, LiF/Al, ITO, etc.
Examples of the compound of the present invention as an electron transport material in a thermally activated delayed fluorescence type organic electroluminescent device are examples 1 to 7; examples as electron transport materials in phosphorescent electroluminescent devices are examples 8 to 14.
Device example 1:
the device structure is as follows:
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/GPH-77：TDE7(30nm,5％wt)/M1(25nm)/LiF(0.5nm)/Al(150nm)。
the preparation process of the organic electroluminescent device is as follows: glass plates coated with ITO (thickness 150nm) transparent conductive layers were sonicated in commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-5～1×10-4Pa, performing vacuum evaporation on the anode layer film to obtain HI-3 and HT-2 which are respectively used as a hole injection layer and a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10nm and 40nm respectively;
vacuum evaporation of "GPH-77: TDE7(30nm, 5% wt)' as the luminescent layer of the organic electroluminescent device, the evaporation rate is 0.1nm/s, and the total film thickness is 30 nm; wherein "5% wt" means the doping ratio of the dye, i.e., the weight ratio of the host material to TDE7 is 95: 5.
Vacuum evaporating M1 on the luminescent layer to form an electron transport layer of the organic electroluminescent device, wherein the evaporation rate is 0.1nm/s, and the total thickness of the evaporation film is 25 nm;
and (3) evaporating LiF with the thickness of 0.5nm as an electron injection layer and Al with the thickness of 150nm as a cathode on the electron transport layer in vacuum.
Device examples 2-7 and comparative examples 1-2 were made as in device example 1, except that the electron transport material was changed to M2, M6, M55, M60, M71, M105 and the prior art materials ET1, AlQ3。
Figure BDA0001790634140000211
Device example 8:
the device structure is as follows:
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/GPH-77：PD1(30nm,5％wt)/M1(25nm)/LiF(0.5nm)/Al(150nm)。
the fabrication process was essentially the same as for device example 1, except that the dye was changed from TDE7 to PD1 and the host material was still GPH-77.
Device examples 9-14 and comparative examples 3-4 were made as in device example 8 except that the electron transport materials were changed to M29, M42, M78, M90, M100, M101 and the prior art materials ET1, AlQ3。
The organic electroluminescent device prepared by the above process was subjected to the following performance measurement:
the turn-on voltage and the maximum luminance of the organic electroluminescent devices prepared in examples 1 to 14 and comparative examples 1 to 4 were measured using a digital source meter and a luminance meter, and the maximum external quantum efficiency was calculated. 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 1cd/m2The voltage is the starting voltage, the current density at the moment is measured, and the maximum external quantum efficiency is calculated according to data such as spectrum and the like.
The maximum brightness, the turn-on voltage, the maximum external quantum efficiency and other relevant properties of the organic electroluminescent device prepared by the above examples are shown in tables 1 to 2 below.
TABLE 1
Figure BDA0001790634140000221
TABLE 2
Figure BDA0001790634140000222
As can be seen from the above table, when the compound of the present invention is used as an electron transport material for TADF and phosphorescent dyes, the turn-on voltage, the maximum luminance, and the maximum external quantum efficiency are all improved, and excellent device performance is shown.
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 (10)

1. A compound of the formula (1):
Figure FDA0001790634130000011
in formula (1):
L1and L2Each independently selected from the group consisting of a single bond, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30One of the heteroaryl groups of (a); preferably, L1、L2Each independently selected from phenyl or pyridyl;
Ar1and Ar2Each independently selected from substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30The heteroaryl group of (a);
and when L is1And L2In the same phase, Ar1And Ar2Different;
F1and F2Each independently selected from hydrogen and C1-C12Alkyl, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30One of the heteroaryl groups of (a);
when the above groups have substituents, the substituents are respectively and independently selected from halogen, cyano, C1-C10Alkyl or cycloalkyl of, C2-C6Alkenyl or cycloalkenyl of1-C6Alkoxy or thioalkoxy of C6-C30Aryl of (C)3-C30One of the heteroaryl groups of (a).
2. The compound of general formula (la) according to claim 1, wherein formula (1) is represented by the following formula (1-1) or formula (1-2):
Figure FDA0001790634130000012
Figure FDA0001790634130000021
in the formula (1-1) or the formula (1-2), L1And L2、F1And F2、Ar1And Ar2Are the same as defined in formula (1).
3. A compound of general formula (la) according to claim 1 or 2, wherein in formula (1), formula (1-1) and formula (1-2):
Ar1selected from the following groups:
Figure FDA0001790634130000022
wherein: x1-X4C, CH or N, and of which up to 2 are N atoms;
a1 and A2 are each independently substituted or unsubstituted C6-C30With condensed ring aryl or substituted or unsubstituted C5-C30The fused ring heteroaryl of (a);
R1and R3Each independently selected from: hydrogen, C1-C10Alkyl radical, C6-C15Aryl of (C)3-C15One of the heteroaryl groups of (a);
wherein "-" indicates that the attachment site is located at any position on the delineated loop structure that is capable of bonding;
Ar2selected from substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30The heteroaryl group of (a).
4. A compound of formula (la) according to claim 3, wherein Ar1A substituent selected from:
Figure FDA0001790634130000031
wherein R is1And R3Each independently selected from: hydrogen, C1-C10Alkyl radical, C6-C15Aryl of (C)3-C15One of the heteroaryl groups of (a);
Figure FDA0001790634130000032
indicating the connection location.
5. A compound of formula (la) according to claim 3, wherein Ar2Selected from the following substituted or unsubstituted groups: triazine group, pyrimidine group, pyridine group, quinazoline group, isoquinazoline group, benzopyrazine group, diphenylphosphine oxide groupAnd a triphenylphosphine oxide group.
6. A compound of formula (la) according to claim 3, wherein Ar2Selected from the following groups:
Figure FDA0001790634130000041
wherein R is1-R3Each independently selected from: hydrogen, C1-C10Alkyl radical, C6-C15Aryl of (C)3-C15One of the heteroaryl groups of (a);
Figure FDA0001790634130000042
indicating the connection location.
7. The compound of general formula (la) according to claim 1 or 2, wherein in formula (1), formula (1-1) and formula (1-2), Ar1Selected from substituted or unsubstituted imidazole groups.
8. A compound of formula (la) according to claim 1 or 2, selected from the compounds of the following specific structures:
Figure FDA0001790634130000043
Figure FDA0001790634130000051
Figure FDA0001790634130000061
Figure FDA0001790634130000071
Figure FDA0001790634130000081
Figure FDA0001790634130000091
9. use of a compound of the general formula according to claim 1 or 2 as electron transport material in an organic electroluminescent device.
10. An organic electroluminescent device comprising a first electrode, a second electrode and one or more organic layers interposed between said first and second electrodes, characterized in that said organic layers comprise at least one compound of formula (la) according to any one of claims 1 or 2.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111574434A (en) * 2020-06-10 2020-08-25 上海天马有机发光显示技术有限公司 Compound, organic light-emitting device comprising compound, display panel and display device
CN111592540A (en) * 2020-06-12 2020-08-28 烟台九目化学股份有限公司 Imidazonaphthyridine high-performance photoelectric material and application thereof
WO2021256871A1 (en) * 2020-06-18 2021-12-23 솔루스첨단소재 주식회사 Organic light-emitting compound and organic electroluminescent device using same
CN114560844A (en) * 2022-04-28 2022-05-31 浙江华显光电科技有限公司 N-heteroaromatic derivative, organic light-emitting device, display panel and display device
WO2022160928A1 (en) * 2021-01-28 2022-08-04 陕西莱特光电材料股份有限公司 Nitrogen-containing compound, and electronic component and electronic device containing same
WO2023204668A1 (en) * 2022-04-22 2023-10-26 주식회사 엘지화학 Novel compound and organic light emitting device comprising same

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009008353A1 (en) * 2007-07-07 2009-01-15 Idemitsu Kosan Co., Ltd. Chrysene derivative and organic el device
WO2010067894A1 (en) * 2008-12-12 2010-06-17 Canon Kabushiki Kaisha Triazine compound and organic light emitting device using the same
KR20120029258A (en) * 2010-09-16 2012-03-26 주식회사 알파켐 Heteroaromatic cycle compound and organic light emitting diode using the same
CN103187531A (en) * 2011-12-30 2013-07-03 昆山维信诺显示技术有限公司 Organic light-emitting device and purpose of double-polarity organic compound
CN103579528A (en) * 2012-07-31 2014-02-12 昆山维信诺显示技术有限公司 Electronic transfer layer, organic light-emitting device comprising electronic transfer layer and manufacturing method of organic light-emitting device
US20150069347A1 (en) * 2013-09-06 2015-03-12 Samsung Display Co., Ltd. Condensed cyclic compound and organic light-emitting device including the same
CN106543149A (en) * 2015-09-16 2017-03-29 三星显示有限公司 Compound and the organic light emitting apparatus including the compound
CN106554319A (en) * 2015-09-30 2017-04-05 北京鼎材科技有限公司 A kind of * analog derivatives containing quinazoline group and its application
CN106554352A (en) * 2015-09-30 2017-04-05 北京鼎材科技有限公司 A kind of condensed-nuclei aromatics derivant containing naphthyridines group and its application
KR20170127379A (en) * 2016-05-11 2017-11-21 주식회사 엘지화학 Heterocyclic compound and organic light emitting device containing the same

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009008353A1 (en) * 2007-07-07 2009-01-15 Idemitsu Kosan Co., Ltd. Chrysene derivative and organic el device
WO2010067894A1 (en) * 2008-12-12 2010-06-17 Canon Kabushiki Kaisha Triazine compound and organic light emitting device using the same
KR20120029258A (en) * 2010-09-16 2012-03-26 주식회사 알파켐 Heteroaromatic cycle compound and organic light emitting diode using the same
CN103187531A (en) * 2011-12-30 2013-07-03 昆山维信诺显示技术有限公司 Organic light-emitting device and purpose of double-polarity organic compound
CN103579528A (en) * 2012-07-31 2014-02-12 昆山维信诺显示技术有限公司 Electronic transfer layer, organic light-emitting device comprising electronic transfer layer and manufacturing method of organic light-emitting device
US20150069347A1 (en) * 2013-09-06 2015-03-12 Samsung Display Co., Ltd. Condensed cyclic compound and organic light-emitting device including the same
CN106543149A (en) * 2015-09-16 2017-03-29 三星显示有限公司 Compound and the organic light emitting apparatus including the compound
CN106554319A (en) * 2015-09-30 2017-04-05 北京鼎材科技有限公司 A kind of * analog derivatives containing quinazoline group and its application
CN106554352A (en) * 2015-09-30 2017-04-05 北京鼎材科技有限公司 A kind of condensed-nuclei aromatics derivant containing naphthyridines group and its application
KR20170127379A (en) * 2016-05-11 2017-11-21 주식회사 엘지화학 Heterocyclic compound and organic light emitting device containing the same

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111574434A (en) * 2020-06-10 2020-08-25 上海天马有机发光显示技术有限公司 Compound, organic light-emitting device comprising compound, display panel and display device
CN111574434B (en) * 2020-06-10 2022-04-15 武汉天马微电子有限公司 Compound, organic light-emitting device comprising compound, display panel and display device
CN111592540A (en) * 2020-06-12 2020-08-28 烟台九目化学股份有限公司 Imidazonaphthyridine high-performance photoelectric material and application thereof
CN111592540B (en) * 2020-06-12 2022-12-27 烟台九目化学股份有限公司 Imidazonaphthyridine high-performance photoelectric material and application thereof
WO2021256871A1 (en) * 2020-06-18 2021-12-23 솔루스첨단소재 주식회사 Organic light-emitting compound and organic electroluminescent device using same
WO2022160928A1 (en) * 2021-01-28 2022-08-04 陕西莱特光电材料股份有限公司 Nitrogen-containing compound, and electronic component and electronic device containing same
WO2023204668A1 (en) * 2022-04-22 2023-10-26 주식회사 엘지화학 Novel compound and organic light emitting device comprising same
CN114560844A (en) * 2022-04-28 2022-05-31 浙江华显光电科技有限公司 N-heteroaromatic derivative, organic light-emitting device, display panel and display device
CN114560844B (en) * 2022-04-28 2022-08-16 浙江华显光电科技有限公司 N-heteroaromatic derivative, organic light-emitting device, display panel and display device

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