CN111620882B - Novel compound for organic electroluminescent device and application - Google Patents
Novel compound for organic electroluminescent device and application Download PDFInfo
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Abstract
Novel compounds for use in organic electroluminescent devices, which compounds are represented by the following general formula (I):
wherein L is1And L3The same or different, are respectively and independently selected from single bond, C6-C30 aromatic hydrocarbon group; ar, R1And R2Each independently selected from hydrogen, halogen, substituted or unsubstituted C6～C30An aromatic hydrocarbon group; r1And R2The same or different; p is an integer of 0 to 6; q is an integer of 0 to 5; n is an integer of 0 to 4. The stable and efficient electronic transmission material prepared by the invention has the advantages of reducing the lighting and working voltage of the device, improving the efficiency of the device, prolonging the service life of the device and having important practical application value.
Description
Technical Field
The invention relates to a novel organic compound and application thereof in the technical field of organic electroluminescent display.
Background
With the increasing maturity of OLED technology and the continuous push in the display field, in order to further improve the competitiveness of OLED technology, the development of OLED materials and the research of novel device structures, which can effectively improve the efficiency and the service life of OLED devices and reduce the driving voltage, have more important meanings.
The excellent new material can obviously reduce the cost of the screen body and improve the efficiency and the service life, thereby more drawing more attention to the research of people on the core material, making outstanding contribution in the aspect of the research by chemists, and designing and developing functional materials with various structures. Generally, electron transport materials are compounds having electron-deficient nitrogen-containing heterocyclic groups, such as compounds containing pyridines, quinolines, imidazoles, thiazoles, pyrimidines, and triazines, which have a high electron affinity and thus a strong ability to accept electrons. At present, the common electron transport materials are AlQ3, BPhen, BCP and some anthracene derivatives, but the efficiency and stability of the electron transport materials still need to be further improved. BPhen and BCP materials suffer from the disadvantage of being easily crystallized. Once the electron transport material is crystallized, the intermolecular charge transition mechanism is different from that of the amorphous film in normal operation, resulting in the change of electron transport properties. When the organic electroluminescent device is used, the conductivity of the whole device is changed, the mobility of electrons and hole charges in the device is unbalanced, the stability of the device is influenced, and the performance of the device is reduced and even fails.
The stable and efficient electronic transmission material is developed, so that the device lighting and working voltage is reduced, the device efficiency is improved, the device service life is prolonged, and the method has important practical application value.
Disclosure of Invention
In order to solve the above problems, the present invention provides a novel class of compounds for organic electroluminescent devices. The compound realizes good electron injection and transmission performance by introducing a novel cyclic amide structure. The compounds of the present invention are represented by the following general formula (I).
Wherein L is1And L3The aryl groups are the same or different and are respectively and independently selected from single bonds and C6-C30 aryl groups (preferably substituted or unsubstituted C6-C20 aryl groups).
Ar、R1And R2Each independently selected from hydrogen, halogen, substituted or unsubstituted C6～C30Aryl (preferably substituted or unsubstituted C)6-C20Aryl) or substituted or unsubstituted C2～C30Heteroaryl (preferably substituted or unsubstituted C)2～C12Heteroaryl, said heteroaryl preferably containing 1 to 2 heteroatoms selected from N).
R1And R2The same or different.
p is an integer of 0 to 6; preferably 1,2, 4, 6.
q is an integer of 0 to 5; preferably 1,2, 3, 4.
n is an integer of 0 to 4; preferably 1, 2.
The halogen may be fluorine, chlorine or bromine.
As the above-mentioned C6～C30Aromatic hydrocarbon group, more preferably C6-C20Preferably said aryl group is a group of the group consisting of phenyl, biphenyl, naphthyl, phenanthryl, triphenylene, fluoranthenyl. The biphenyl group is selected from the group consisting of 2-biphenyl group and 3-biphenyl group, the naphthyl group is selected from the group consisting of 1-naphthyl group and 2-naphthyl group, the phenanthryl group is selected from the group consisting of 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group and 9-phenanthryl group, and the triphenylene group is selected from the group consisting of 1-triphenylene group and 2-triphenylene group.
As the above-mentioned C2～C30Heteroaryl, preferably substituted or unsubstituted C2～C12Heteroaryl, said heteroaryl preferably containing 1 to 2 heteroatoms selected from N, including pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, benzimidazolyl, phenanthrothiazolyl, quinolinyl, isoquinolinyl, quinazolinyl, phenanthrolinyl, triazinyl, oxadiazolyl.
Further, L1And L3The same or different, are respectively and independently selected from the group consisting of mono, phenylene, biphenylene and naphthylene.
Ar is selected from hydrogen, fluorine, chlorine, bromine, phenyl, naphthyl, biphenyl, terphenyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, 1-triphenylene, 2-triphenylene, fluoranthenyl, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, benzimidazolyl, phenanthrothiazolyl, quinolyl, isoquinolyl, quinazolinyl, phenanthrolinyl, triazinyl, oxadiazolyl.
R1And R2Each independently selected from hydrogen, fluorine, chlorine, bromine, phenyl, naphthyl, biphenyl, terphenyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, 1-triphenylene, 2-triphenylene, fluoranthenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, benzimidazolyl, phenanthrothiazolyl, quinolyl, isoquinolyl, quinazolinyl, phenanthroline, triazinyl, oxadiazolyl.
The substituents on the aromatic hydrocarbon group and the heteroaryl group, which may be the same or different, are independently selected from the group consisting of C6-C20 aromatic hydrocarbon groups, examples of which include phenyl, biphenyl, terphenyl, and naphthyl;
the number of the substituents is 1,2, 3, 4,5, 6 or more.
Further, it is represented by the following general formula (II).
Wherein, Ar and R1、L1、L2P and n are as defined for formula (I).
In the present invention, Ca-CbThe expression (b) represents that the group has the number of carbon atoms of a to b, and generally the number of carbon atoms does not include the number of carbon atoms of the substituent unless otherwise specified.
In the present invention, the expression of chemical elements includes the concept of chemically identical isotopes, such as the expression of "hydrogen", and also includes the concept of chemically identical "deuterium" and "tritium".
The compound of the general formula uses a cyclic amide structure formed by carbazole as a mother nucleus, on one hand, the carbonyl group of amide has good electron affinity, so that the injection of electrons is easier, on the other hand, lone pair electrons on N atoms form effective accumulation through conjugated bonds in a special form, and the HOMO energy level and LUMO energy level of molecules can be adjusted through the selection of substituent groups on the carbazole unit and the benzoyl unit, so that the carrier mobility is improved.
The invention also discloses application of the cyclic amide derivative in preparing an organic electroluminescent device.
The cyclic amide derivative is used as an electron transport material.
The invention also discloses an organic electroluminescent device, which comprises a substrate, and an anode layer, an organic light-emitting functional layer and a cathode layer which are sequentially formed on the substrate;
the organic light-emitting functional layer comprises a hole injection layer, a hole transport layer, an organic light-emitting layer and an electron transport layer;
the electron transport material of the electron transport layer comprises at least one of the cyclic amide derivative materials.
Detailed Description
The organic electroluminescent compounds according to the present invention, the preparation method thereof, and the preparation method and light emitting properties of a light emitting device comprising the same are described in detail below with reference to the following examples.
Various chemicals used in the present invention, such as petroleum ether, ethyl acetate, tetrahydrofuran, n-hexane, toluene, acetic acid, methylene chloride, DMF, methyl o-iodobenzoate benzene, tetrakistriphenylphosphine palladium, dimethyl 4, 5-dibromophthalate, phenylboronic acid, p-tolylboronic acid, 2-naphthylboronic acid, p-fluorophenylboronic acid, 4-biphenylboronic acid, 4-pyridineboronic acid, 1, 2-cyclohexanedione, phenylhydrazine hydrochloride, 6-bromonaphthalen-2-ylhydrazine hydrochloride, isoamylnitrite, zinc powder, sodium sulfate, and the like, are commercially available in domestic chemical product markets.
Synthesis example 1 preparation of intermediate M1
Synthesis of intermediate M1-1: 22.5 g of 8-bromo-1-tetralone (0.1mol), 18.0 g of methyl benzoate-2-boronic acid (0.10mol), 1.15g of tetrakistriphenylphosphine palladium (1mmol), 31.8 g of sodium carbonate (0.3mol)100ml of toluene, 100ml of ethanol and 120ml of water were added to a three-necked flask equipped with a condenser tube under nitrogen protection, and the reaction system was heated to reflux with stirring, followed by TLC monitoring and completion of the reaction for about 6 hours. After cooling, water was added for liquid separation, extraction, organic layers were combined, dried, and column chromatography was performed to obtain 23.5g of white solid M1-1 with a yield of 84%.
Synthesis of intermediate M1-2: a1 liter reaction flask was charged with 14.0g (50mmol) of M1-1 prepared above and 14.7g (60mmol) of 6-bromo-2-naphthylhydrazine hydrochloride, dissolved in 200ml of ethanol, and then 0.3g (3.1mmol) of concentrated sulfuric acid was added to the above solution, and the solution was stirred at 65 ℃ for 4 hours. The reaction was cooled to room temperature and the brown precipitate was filtered, washed twice with ethanol and dried under reduced pressure to give a brown solid. Dissolving the solid into a mixed solution of 200g of acetic acid and 20g of trifluoroacetic acid, stirring the reaction system at 100 ℃ for reacting for 15 hours, cooling the reaction system to room temperature, separating out light yellow solid, filtering the solid, washing the solid with 200ml of acetic acid and 200ml of n-hexane respectively, and purifying the solid by silica gel column chromatography to obtain a light yellow solid intermediate 10.8 g of M1-2 with the yield of 45%.
Synthesis of intermediate M1: in a 250ml three-necked flask, 100ml dry DMF and 12 g M1-2(25mmol) were added, the solution was cooled to 0 ℃ and NaH (1.2g, 60% content, 30mmol) was slowly added to release a large amount of bubbles, after the addition, the reaction was stirred at low temperature for 30 minutes, then the reaction system was heated to 80 ℃ and stirred for 4 hours, and the completion of the reaction was monitored by TLC. After cooling, a saturated ammonium chloride solution is added for quenching, liquid separation and extraction are carried out, organic layers are combined, drying and column chromatography separation are carried out, and 9.1 g of intermediate M1 is obtained.
The yield thereof is 81%
Product MS (m/e): 447 elemental analysis (C27H14 BrNO): theoretical calculation value C: 72.34%, H: 3.15%, N: 3.12 percent; found value C: 72.47%, H: 3.23%, N: 3.09 percent.
Synthetic example 2 preparation of intermediate M2
Intermediate M2 was prepared according to the same procedure as in Synthesis example 1, except that methyl benzoate-2-boronic acid in the first step was replaced with an equivalent amount of methyl benzoate 4-bromo-2-boronic acid and 8-bromo-1-tetralone was replaced with 8-iodo-1-tetralone to give intermediate M2.
Product MS (m/e): 525, elemental analysis (C27H13Br2 NO): theoretical calculation value C: 61.51%, H: 2.49%, N: 2.66 percent; found value C: 61.62%, H: 2.38%, N: 2.69 percent.
Synthetic example 3 preparation of intermediate M3
Intermediate M3 was prepared in the same manner as in Synthesis example 1, except that methyl benzoate-2-boronic acid in the first step was replaced with an equivalent amount of methyl benzoate 4-bromo-2-boronic acid and 8-bromo-1-tetralone was replaced with 8-iodo-4-bromo-1-tetralone, to give intermediate M3.
Product MS (m/e): 603, elemental analysis (C27H12Br3 NO): theoretical calculation value C: 53.50%, H: 2.00%, N: 2.31 percent; found value C: 53.52%, H: 2.02%, N: 2.28 percent.
Synthetic example 4 preparation of intermediate M4
Intermediate M3 was prepared in the same manner as in Synthesis example 1, except that methyl benzoate-2-boronic acid in the first step was replaced with an equivalent amount of methyl benzoate 4-bromo-2-boronic acid and 8-bromo-1-tetralone was replaced with 8-iodo-4-chloro-1-tetralone to give intermediate M4.
Product MS (m/e): 559, elemental analysis (C27H12Br2 ClNO): theoretical calculation value C: 57.74%, H: 2.15%, N: 2.49 percent; found value C: 57.69%, H: 2.21%, N: 2.61 percent.
Synthesis example 5 preparation of Compound A1
Synthesis of intermediate A3-1: to a 500ml three-necked flask equipped with stirring were added intermediate M1(22.4g, 0.05mol), 3, 5-dichlorophenylboronic acid (10.5g, 0.055mol), Pd (PPh)3)4(1.15g, 1mmol), anhydrous sodium carbonate (10.6g, 0.1mol), toluene (100ml), ethanol (60ml), water (100 ml). Under the protection of nitrogen, the reaction mixture is mechanically uniform, and the reaction mixture is heated to reflux. And (3) refluxing for 10 hours, monitoring the reaction by TLC, stopping the reaction, and cooling. 100ml of ethyl acetate is added into the reaction system, liquid separation is carried out, the water phase is washed twice by 100ml of ethyl acetate, the organic phases are combined, dried by anhydrous sodium sulfate, then the solvent is pumped out, and the residue is separated by column chromatography to obtain 22.2 g of light yellow intermediate A3-1 with the yield of 86%.
Synthesis of compound a 3: a solution of A3-1(25.7g, 0.05mol), 4-pyridineboronic acid (14.8g, 0.12mol), cesium carbonate (78g, 0.24mol) and dioxane 500ml were placed in a 1L three-necked flask with magnetic stirring and nitrogen substitution in this order, and stirring was started. After nitrogen replacement again, (1.1g, 5.5mmol) tri-tert-butylphosphine and (1.27g, 2.2mmol) bis (dibenzylideneacetone) palladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 8 hours, and reducing the temperature after the TLC monitoring reaction is finished. Adjusting pH to neutral, separating organic phase, extracting, drying, performing column chromatography, and spin-drying solvent to obtain 20.7g pale yellow solid with yield of about 69%.
Product MS (m/e): 599; elemental analysis (C)43H25N3O): theoretical value C: 86.12%, H: 4.20%, N: 7.01 percent; found value C: 86.23%, H: 4.16%, N: 6.95 percent
Synthesis example 6 preparation of Compound A15
In a 1l three-necked flask equipped with stirring, intermediate M2(26.3g, 0.05mol), 2-phenylquinazoline-4-boronic acid (27.5g, 0.11mol), Pd (PPh) were added3)4(2.3g, 2mmol), anhydrous sodium carbonate (21.2g, 0.2mol), toluene (200ml), ethanol (120ml), water (200 ml). Reacting and mixing under the protection of nitrogenThe materials are mechanically uniform, and are started to be heated until the materials are refluxed. And (3) refluxing for 5 hours, monitoring the reaction by TLC, stopping the reaction, and cooling. 300ml of ethyl acetate was added to the reaction system, liquid separation was performed, the aqueous phase was washed twice with 300ml of ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, then the solvent was drained off, and the residue was separated by column chromatography to give 26.8 g of pale yellow intermediate a15, yield 69%.
Product MS (m/e): 777; elemental analysis (C)55H31N5O): theoretical value C: 84.92%, H: 4.02%, N: 9.00 percent; found value C: 84.79%, H: 4.10%, N: 8.95 percent
Device application example
In order to further illustrate the application of the material of the invention as an electron transport material in an OLED device and compare the performance of the material with the performance of a common electron transport material, the invention adopts the following simple electroluminescent device, and the specific structure of the organic electroluminescent device in the application example of the device of the invention is as follows:
ITO/2-TNATA/NPB/CBP:(piq)2Ir(acac)(1:5％)/ETL/LiF/Al
the hole injection material adopts 2-TNATA; the hole transport material used was commonly used NPB; the material of the luminescent layer uses red phosphorescent dye (piq)2Ir (acac), collocated with a red light subject CBP; the electron transport layer used for comparison is made of a common electron transport material Bphen. The structural formula of the material used for each functional layer is as follows:
the substrate may be a substrate used in a conventional organic light emitting device, for example: glass or plastic. In the invention, the glass substrate and the ITO are used as anode materials in the manufacture of the organic electroluminescent device.
Various triarylamine materials can be used for the hole transport layer, and the hole transport material selected for use in the fabrication of the organic electroluminescent device of the present invention is NPB.
The cathode can adopt metal and a mixture structure thereof, such as Mg: Ag, Ca: Ag and the like, and can also be an electron injection layer/metal layer structure, such as common cathode structures of LiF/Al, Li2O/Al and the like. The cathode material selected in the preparation of the organic electroluminescent device is LiF/Al.
Device example 1 compound a1 of the invention was used as an electron transport material:
the ITO (150nm) transparent conductive layer coated glass plate was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent (volume ratio is 1: 1), baking in a clean environment until 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 × 10-5-9×10-3Pa, evaporating a compound 2-TNATA on the anode layer film in vacuum to form a hole injection layer with the thickness of 60 nm; evaporating a compound NPB on the hole injection layer in vacuum to form a hole transport layer with the thickness of 20nm, wherein the evaporation rate is 0.1 nm/s;
forming an electroluminescent layer on the hole transport layer, and specifically operating as follows: placing CBP [4,4'-N, N' -dicarbazole-biphenyl as a host material of a light-emitting layer in a cell of a vacuum vapor deposition apparatus, to be (piq) as a dopant2Ir (acac) [ bis- (1-phenylisoquinolinyl) acetylacetonatoiridium (III)]Placing in another chamber of the vacuum vapor deposition apparatus, simultaneously evaporating two materials at different rates, (piq)2The concentration of Ir (acac) is 5 percent, and the total film thickness of evaporation plating is 30 nm;
vacuum evaporating the compound A1 of the invention on the luminescent layer to form an electron transport layer with a thick film of 20nm, wherein the evaporation rate is 0.1 nm/s;
LiF with the thickness of 0.5nm is vacuum-evaporated on the Electron Transport Layer (ETL) to be used as an electron injection layer, and an Al layer with the thickness of 150nm is used as a cathode of the device.
And carrying out packaging test on the prepared device.
Device example 2 compound a3 of the invention was used as an electron transport material:
referring to the preparation method of device example 1, compound A3 of the present invention was used instead of compound a1 as an electron transporting material.
Device example 3 compound a10 of the invention was used as an electron transport material:
referring to the preparation method of device example 1, compound a10 of the present invention was used instead of compound a1 as an electron transporting material.
Device example 4 compound a17 of the invention was used as an electron transport material:
referring to the preparation method of device example 1, compound a17 of the present invention was used instead of compound a1 as an electron transporting material.
Device example 5 compound a19 of the invention was used as an electron transport material:
referring to the preparation method of device example 1, compound a19 of the present invention was used instead of compound a1 as an electron transporting material.
Device example 6 compound a21 of the invention was used as an electron transport material:
referring to the preparation method of device example 1, compound a21 of the present invention was used instead of compound a1 as an electron transporting material.
Comparative device example 1 use of Bphen as an electron transport material
Referring to the preparation method of device example 1, compound Bphen was used as an electron transport material instead of compound a 1.
Comparative device example 2 use B as an electron transport material
Referring to the preparation method of device example 1, compound B was used as an electron transport material instead of compound a 1.
The voltage and current efficiencies of the organic electroluminescent devices prepared in the respective application examples were measured at the same luminance, and the measurement results are shown in table 1 below.
TABLE 1 results of measurements of devices using the compounds of the invention as electron transport layers and/or as luminescent host materials
| Device numbering | ETL material | Required luminance cd/m2 | Voltage V | Current efficiency cd/A |
| Device example 1 | A1 | 2000 | 4.9 | 10.8 |
| Device example 2 | A3 | 2000 | 5.1 | 11.7 |
| Device example 3 | A10 | 2000 | 5.0 | 11.2 |
| Device example 4 | A17 | 2000 | 4.8 | 12.4 |
| Device example 5 | A19 | 2000 | 4.8 | 12.2 |
| Device example 6 | A21 | 2000 | 4.9 | 11.4 |
| Comparison device 1 | Bphen | 2000 | 5.7 | 8.9 |
| Comparison device 1 | B | 2000 | 4.8 | 10.2 |
From the experimental data in table 1, compared with the comparative device examples 1 and 2, the novel organic material of the present invention is used as an electron transport material in an organic electroluminescent device, can effectively reduce the working voltage of the device, improve the current efficiency, and is an electron transport material with good performance. This is related to the higher electron affinity and the higher electron mobility and the good thermal stability of the material of the present invention.
The above examples only list the effect data of a1, A3, a10, a17, a19 and a21, which are representative sampling tests, and the overall data are not very different from each other by experimental data, and can directly represent the effects of other non-listed a2, a4-a9, a11-a16, a18 and a20-a 22.
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 (8)
1. A compound for use in an organic electroluminescent device, characterized in that: the compounds are represented by the following general formula (II):
wherein L is1、L3The same or different, are respectively and independently selected from single bond and C6～C30An aromatic hydrocarbon group;
Ar、R1each independently selected from hydrogen, halogen, substituted or unsubstituted C6～C30An aromatic hydrocarbon group; said C is6～C30The aromatic hydrocarbon group is selected from the group consisting of phenyl, biphenyl, naphthyl, phenanthryl, fluoranthenyl;
p is an integer of 0 to 6;
n is an integer of 0 to 4.
2. The compound of claim 1, wherein: the biphenyl group is selected from the group consisting of 2-biphenyl group and 3-biphenyl group, the naphthyl group is selected from the group consisting of 1-naphthyl group and 2-naphthyl group, and the phenanthryl group is selected from the group consisting of 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group and 9-phenanthryl group.
3. The compound of claim 1, wherein: ar is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, phenyl, naphthyl, biphenyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, and 9-phenanthryl.
4. The compound of claim 1, wherein: r1Selected from the group consisting of hydrogen, fluoro, chloro, bromo, phenyl, naphthyl, biphenyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, and 9-phenanthryl.
5. A compound characterized by: the compounds are as follows:
6. the compound of claim 1, wherein: the compound forms a cyclic amide derivative by taking a cyclic amide structure formed by a carbazole unit as a parent nucleus, on one hand, the carbonyl group of the amide has good electron affinity so that electrons are easy to inject, on the other hand, lone-pair electrons on an N atom form accumulation through conjugated bonds, and the HOMO energy level and LUMO energy level of molecules can be adjusted by selecting substituents on the carbazole unit and a benzoyl unit, so that the carrier mobility is improved.
7. Use of a compound according to claim 6 for the preparation of an organic electroluminescent device, characterized in that: the compounds are useful as electron transport materials.
8. Use of a compound according to claim 7 for the preparation of an organic electroluminescent device, characterized in that: the organic light-emitting diode comprises a substrate, and an anode layer, an organic light-emitting functional layer and a cathode layer which are sequentially formed on the substrate; the organic light-emitting functional layer comprises a hole injection layer, a hole transport layer, an organic light-emitting layer and an electron transport layer; the electron transport material of the electron transport layer comprises at least one of the compounds.
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