CN113105491A - Pyridine diphenoxyl boron fluoride compound, application thereof and organic electroluminescent device containing compound - Google Patents
Pyridine diphenoxyl boron fluoride compound, application thereof and organic electroluminescent device containing compound Download PDFInfo
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- CN113105491A CN113105491A CN202110395607.4A CN202110395607A CN113105491A CN 113105491 A CN113105491 A CN 113105491A CN 202110395607 A CN202110395607 A CN 202110395607A CN 113105491 A CN113105491 A CN 113105491A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 64
- -1 Pyridine diphenoxyl boron fluoride compound Chemical class 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 128
- 230000000903 blocking effect Effects 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- 125000001424 substituent group Chemical group 0.000 claims description 13
- 230000005525 hole transport Effects 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 229910052805 deuterium Inorganic materials 0.000 claims description 7
- 125000004431 deuterium atom Chemical group 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
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- XFAZZQREFHAALG-UHFFFAOYSA-N N-{1-amino-6-[(5-nitro-2-furoyl)amino]-1-oxohexan-2-yl}-23-(indol-3-yl)-20-oxo-4,7,10,13,16-pentaoxa-19-azatricosan-1-amide Chemical compound C=1NC2=CC=CC=C2C=1CCCC(=O)NCCOCCOCCOCCOCCOCCC(=O)NC(C(=O)N)CCCCNC(=O)C1=CC=C([N+]([O-])=O)O1 XFAZZQREFHAALG-UHFFFAOYSA-N 0.000 description 4
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- 229910000024 caesium carbonate Inorganic materials 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
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- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
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- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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Abstract
The invention discloses a pyridine diphenoxyl boron fluoride compound, application thereof and an organic electroluminescent device containing the compound, wherein the pyridine diphenoxyl boron fluoride compound has a structure shown by the combination of a formula (1) and a formula (2), and X in the structure shown by the formula (2)1～X8Are each independently selected from CR12Or N; y is1And Y2Are each independently selected from CR13R14、CR15CR16、SiR17R18、NR19O, S, wherein Y is2But also a single bond or a hydrogen bond. The compound provided by the invention can be used as a luminescent material, a host material, a hole blocking material or an electron transport material of an organic electroluminescent deviceThe thermal activation delayed fluorescence material has higher radiation rate or/and excellent electron transmission performance, and improves the efficiency and the service life of the organic electroluminescent device.
Description
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to a novel organic compound, application thereof and an organic electroluminescent device containing the compound.
Background
An Organic Light Emitting Device (OLED) is a current-driven thin film device with a sandwich-like structure, and a single layer or multiple layers of Organic functional material are sandwiched between an anode and a cathode. Under the action of an electric field, holes generated by an anode and electrons generated by a cathode move to be respectively injected into a hole transport layer and an electron transport layer and migrate to a light emitting layer, and when the holes and the electrons meet and are combined at the light emitting layer, energy excitons are generated, so that light emitting molecules are excited to finally generate visible light. The OLED has the characteristics of self-luminescence, wide visual angle, wide color gamut, short response time, high luminous efficiency, low working voltage, low cost, simple production process and the like, can be manufactured into a large-size and/or flexible ultrathin panel, is a novel display technology with rapid development and higher process integration level, is widely applied to display products such as televisions, smart phones, tablet computers, vehicle-mounted display, illumination and the like at present, and is further applied to creative display products such as large-size display, flexible screens and the like.
The organic photoelectric material applied to the OLED device may be divided into a light emitting layer material and an auxiliary functional layer material in terms of application, wherein the light emitting layer material includes a guest material (also called a light emitting material or a dopant material) and a host material (also called a host material), the light emitting material is divided into a Fluorescent material, a phosphorescent material and a Thermally Activated Delayed Fluorescence (TADF) material according to different energy transfer modes, and the auxiliary functional layer material is divided into an electron injecting material, an electron transporting material, a hole blocking material, an electron blocking material, a hole transporting material and a hole injecting material according to the property that the electron or hole transport speed is different.
The fluorescent material has the advantages of low production cost and high emission rate, but the fluorescent material can only utilize the energy of a non-spin-symmetric singlet excited state, and the energy only accounts for 25% of the energy generated after electron-hole recombination, so the limit of the internal quantum efficiency is 25%. Although the phosphorescent material can utilize the strong spin-orbit coupling of heavy metal atoms to effectively promote the intersystem crossing of electrons from the singlet state to the triplet state, so that all energy of singlet-state and triplet-state excitons generated by electric excitation can be fully utilized, the internal quantum efficiency can reach 100%, the emission rate is slow, and rare metals such as iridium are generally used, and the production cost is increased. The TADF material with a small singlet-triplet energy gap is excited by using heat in the surrounding environment by combining the advantages of the two types of luminescent materials, so that the exciton can be crossed from a triplet state to a singlet state in a reverse system, the internal quantum efficiency can reach 100% theoretically, and the production cost is low because rare metal is not used.
Although the efficiency of the current TADF materials is already comparable to that of phosphorescent materials, the device lifetime is still insufficient for practical applications. Current studies show that, in addition to factors such as reverse-system-interface bouncing rate and chemical stability, the fluorescence radiation rate constant (j. mater. chem.c,2018,6, 7728-7733) of TADF molecules and the electron transport property (adv. electron. mater.2019,5,1800708) thereof have a great influence on the service life of devices.
Therefore, there is a need in the art to develop a new type of thermally activated delayed fluorescence material with high radiation rate constant and/or high electron transport property, which can be used to produce an organic electroluminescent device with high efficiency and long lifetime under low driving voltage.
Disclosure of Invention
In order to solve the technical problems, the invention provides a novel pyridine diphenoxy boron fluoride organic compound which has a structure shown by the combination of a formula (1) and a formula (2):
wherein,
the substituent represented by the formula (2) is only in R of the formula (1)2、R3、R9Or R10Position by a-and R2、R3、R9Or R10The positions are linked by keys;
in the formula (2), p and q are each independently an integer of 1 to 4;
further, p and q are required to be each independently an integer of 1 to 2;
in the formula (2), L is independently selected from a single bond, a substituted or unsubstituted straight chain or branched chain alkylene group with 1-20 carbon atoms, a substituted or unsubstituted cycloalkylene group with 3-20 ring carbon atoms, a substituted or unsubstituted arylene group with 6-30 ring carbon atoms, a substituted or unsubstituted heteroarylene group with 2-30 ring carbon atoms, a substituted or unsubstituted fused aryl ring with 10-50 ring carbon atoms, and a substituted or unsubstituted fused heterocyclic ring with 6-50 ring carbon atoms;
further, L is independently selected from a single bond, or any one or more of the following substituted or unsubstituted groups: pyridylene, phenylene, biphenylene, naphthylene, anthracenylene.
In the formula (2), X1～X8Are each independently selected from CR12Or N;
further, X is required1～X8The number of nitrogen atoms in (b) is an integer of 0 to 5, preferably an integer of 0 to 3;
in the formula (2), Y1And Y2Are each independently selected from CR13R14、CR15CR16、SiR17R18、NR19O, S, wherein Y is2Can also be selected as single bond or hydrogen bond;
r of formula (1)1～R11R of the formula (2)12～R19Each of the substituent groups is independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, a substituted amino group, a substituted silyl group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted aryl groupA 1-valent heterocyclic group having 5 to 50 ring atoms;
adjacent R1～R19The substituent groups can be bonded with each other to form a substituted or unsubstituted saturated or unsaturated ring, and can also form a substituted or unsubstituted saturated or unsaturated fused ring with an adjacent aromatic ring or heteroaromatic ring;
further, R1～R19The substituent groups are respectively and independently any one or more of the following groups: a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, a substituted amine group, a substituted silyl group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted indenofluorenyl group, a substituted or unsubstituted fluoranthryl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted perylene group, a substituted or unsubstituted amino group, a substituted or unsubstituted silyl group, a substituted
A phenyl group, a substituted or unsubstituted tetracenyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted dibenzothiazolyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzoselenophenyl group, a substituted or unsubstituted carbazolyl group;
further, the condensed ring group described in the formula (2) may be preferably selected from the group shown below: :
when the above groups have substituents, the substituents are independently selected from deuterium atom, halogen atom, cyano group, nitro group, hydroxyl group, 1-valent arylamine group with 7-30 carbon atoms, 1-valent silicon group with 3-30 carbon atoms, 1-valent alkyl or cycloalkyl group with 1-10 carbon atoms, 1-valent monocyclic aryl or condensed ring aryl with 6-30 carbon atoms, 1-valent heterocyclic group with 2-50 carbon atoms or condensed ring heteroaryl;
further, the substituents on the groups are respectively and independently selected from any one or more of the following substituents: deuterium atom, halogen atom, cyano group, nitro group, hydroxyl group, dimethyltriarylamine group, diphenyltriarylamine group, trimethylsilyl group, triphenylsilyl group, methyl group, methoxy group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-methylbutyl group, cyclohexyl group, adamantyl group, 2-ethylhexyl group, trifluoromethyl group, pentafluoroethyl group, 2,2, 2-trifluoroethyl group, phenyl group, deuterated phenyl group, fluorophenyl group, methylphenyl group, n-propylphenyl group, tert-butylphenyl group, trimethylphenyl group, triphenylphenyl group, tetraphenylphenyl group, cyanophenyl group, naphthyl group, anthracenyl group, biphenylyl group, terphenyl group, fluorenyl group, spirobifluorenyl group, furyl group, benzofuryl group, dibenzofuryl group, azabenzofuryl group, thienyl group, benzothienyl group, dibenzothienyl, Carbazolyl, phenylcarbazolyl, azacarbazolyl.
Further, the compounds represented by the combination of the formula (1) and the formula (2) according to the present invention may preferably be represented by the following specific structural compounds 1 to 164:
the second objective of the present invention is to provide an organic electroluminescent device. The organic electroluminescent device comprises an anode, a cathode and at least one layer of organic thin film arranged between the anode and the cathode, wherein the organic thin film contains one or more organic electroluminescent compounds represented by the combination of the formula (1) and the formula (2). The organic layer comprises a light-emitting layer and a functional layer, and the compound represented by the combination of the formula (1) and the formula (2) can be used as a host material of the light-emitting layer alone, can be used as a light-emitting material of the light-emitting layer alone, can be mixed with other host materials for use, can be used as an electron transport layer material, and/or can be used as a hole blocking layer material alone or in a mixture.
When the compound represented by the combination of the formula (1) and the formula (2) is used as a phosphorescent host material in the light-emitting layer, the kind or the amount of the light-emitting material is not limited, and the light-emitting layer may be used as a host for a red phosphorescent material or a green phosphorescent material.
It is a further object of the present invention to provide an organic electroluminescent device. When the compound represented by the combination of the formula (1) and the formula (2) is applied to a device, an organic electroluminescent device with higher luminous efficiency and longer service life at low driving voltage is obtained by optimizing the structure of the device.
The beneficial effects of the invention include:
the compound protected by the invention is a pyridine diphenoxy boron fluoride compound, and the combination of the pyridine diphenoxy boron fluoride unit and the group represented by the formula (2) can realize high-radiation-rate thermal activation delayed fluorescence, thereby improving the efficiency and the service life of the organic electroluminescent device.
When the compound protected by the invention is applied to an organic electroluminescent device, the pyridine diphenoxy boron fluoride group has excellent electron transport property, so that the compound is used as an electron transport material, a hole blocking material and/or a main material, and the organic electroluminescent device manufactured by the compound has the improvement effects of improving efficiency and prolonging service life.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
FIG. 1 is a schematic diagram of the structure of an organic electroluminescent device to which the compound of the present invention is applied, wherein the structures of the layers of the device represent the following meanings:
1. a transparent substrate layer, 2, an ITO anode layer, 3, a hole injection layer, 4, a hole transport layer A, 5, a hole transport layer B (or an electron blocking layer), 6, a light-emitting layer, 7, an electron transport layer B (or a hole blocking layer), 8, an electron transport layer A, 9, an electron injection layer, 10 and a cathode reflecting electrode layer;
FIG. 2 is a fluorescence decay spectrum of chemical 2 doped mCBP film;
fig. 3 shows fluorescence decay spectrum of chemical-11 doped mCBP thin film.
Detailed Description
The principles and features of this invention will be further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention.
The synthesis of the specific compounds of the combinations of formula (1) and formula (2) listed below, unless otherwise indicated, is carried out in an anhydrous solvent under a protective gas atmosphere.
Synthesizing an intermediate: synthesis of intermediate 1d
Synthesis of 1 a: 3.2g (20.5mmol,1.02eq) of 2-methoxyphenylboronic acid, 3.8g (20mmol,1.0eq) of 2-chloro-6-bromopyridine, 0.46g (0.4mmol,0.02eq) of tetratriphenylphosphine palladium and 5.5g (40mmol,2.0eq) of potassium carbonate were weighed into a flask, evacuated, protected with nitrogen, deoxygenated 30ml of toluene, 8ml of ethanol and 5ml of water were added, and the mixture was refluxed at 90 ℃ for 12 hours. The reaction was stopped, cooled to room temperature, extracted with ethyl acetate, washed three times with water, concentrated in solvent, and separated on silica gel column to give 3.90g of white solid 1a with 90% yield.
Synthesis of 1 b: 3.9g (18mmol,1.0eq) of 1a,3.2g (18.9mmol,1.05eq) of 4-fluoro-2-methoxyphenylboronic acid, 0.33g (0.36mmol,0.02eq) of tris (dibenzylideneacetone) dipalladium, 0.66g (2.16mmol,0.12eq) of tris (o-tolylene-phosphine, 5.0g (36mmol,2.0eq) of potassium carbonate were weighed into a flask, purged with air, protected with nitrogen, deoxygenated 40ml of tetrahydrofuran, 8ml of water were added, and the mixture was refluxed at 80 ℃ for 12 hours. The reaction was stopped, cooled to room temperature, extracted with ethyl acetate, washed three times with water, concentrated in solvent, and separated on silica gel column to give 5.4g of white solid 1b in 97% yield.
Synthesis of 1 c: 5.4g (17.5mmol,1.0eq) of 1b, 20.0g (175mmol,10.0eq) of pyridine hydrochloride were weighed into a flask, stirred at 180 ℃ for 5h under nitrogen protection. Cooling to room temperature, neutralizing with sodium hydroxide solution, precipitating a large amount of solid, filtering, washing with water, collecting the filter cake, dispersing in methanol, stirring, filtering, and drying to obtain 4.67g of white solid 1c with a yield of 95%.
1d Synthesis: weighing (16.6mmol,1.0eq)1c, dissolving in 40ml dichloromethane, nitrogen protecting, adding dropwise 18.9g (133mmol,8.0eq) boron trifluoride diethyl ether and then 8.56g (66.4mmol, 4.0eq) N, N-diisopropylethylamine in an ice-water bath; after the addition was complete, the mixture was stirred at room temperature for 2 hours. The reaction was stopped and sodium carbonate solution was added to neutralize the reaction. The reaction solution was extracted with dichloromethane, concentrated by rotary evaporation, and methanol was added to precipitate a pale yellow solid, which was collected by filtration and dried to give 4.92g of pale yellow solid 1d with a yield of 96%.
In the same synthesis method, other intermediates can be obtained by replacing 2-methoxyphenylboronic acid with the raw materials in table 1, as shown in table 1:
TABLE 1
Synthesizing an intermediate: synthesis of intermediate 4c
4a Synthesis: 3.81g (20.5mmol,2.05eq) of 2-methoxy-4-chlorobenzeneboronic acid, 2.37g (10mmol,1.0eq) of 2, 6-dibromopyridine, 0.34g (0.3mmol,0.03eq) of tetratriphenylphosphine palladium and 5.5g (40mmol,4.0eq) of potassium carbonate were weighed into a flask, purged, protected with nitrogen, charged with deoxygenated 30ml of toluene, 8ml of ethanol and 5ml of water, and reacted at 90 ℃ under reflux for 12 hours. The reaction was stopped, cooled to room temperature, extracted with ethyl acetate, washed three times with water, concentrated in solvent, and isolated on silica gel column to give 3.28g of white solid 4a in 91% yield.
4b Synthesis: 3.24g (9mmol,1.0eq) of 1b, 10.35g (90mmol,10.0eq) of pyridine hydrochloride were weighed into a flask, stirred at 180 ℃ for 5h under nitrogen protection. Cooling to room temperature, neutralizing with sodium hydroxide solution, precipitating a large amount of solid, filtering, washing with water, collecting filter cake, dispersing in methanol, stirring, filtering, and drying to obtain 2.84g of white solid 4b with yield of 95%.
4c Synthesis: weighing 3.3g (10mmol,1.0eq) of 4b in 40ml of dichloromethane, adding 11.4g (80mmol,8.0eq) of boron trifluoride diethyl ether dropwise in an ice-water bath under the protection of nitrogen, and adding 5.16g (40mmol,4.0eq) of N, N-diisopropylethylamine dropwise; after the addition was complete, the mixture was stirred at room temperature for 2 hours. The reaction was stopped and sodium carbonate solution was added to neutralize the reaction. The reaction solution was extracted with dichloromethane, concentrated by rotary evaporation, and methanol was added to precipitate a pale yellow solid, which was collected by filtration and dried to give 3.30g of pale yellow solid 4c with a yield of 92%.
In the same synthesis method, other intermediates can be obtained by replacing 2-methoxyphenylboronic acid with the raw materials in table 2, as shown in table 2:
TABLE 2
Synthesis example 1: synthesis of formula 2
1.55g (5.0mmol, 1.0eq) of intermediate 1d, 1.75g (5.5mmol, 1.1eq) of diphenylcarbazole, 3.26g (10.0mmol, 2.0eq) of cesium carbonate were weighed, 20ml of dry DMF was added, and the reaction was carried out at 120 ℃ for 10 hours. The reaction was stopped, cooled to room temperature, poured into 100ml of water, and a yellow solid precipitated, filtered and washed with water. The filter cake was collected, recrystallized from dichloromethane/methanol, filtered and dried to give 2.74g of a yellow solid in 90% yield, ms M/z 609.5(M + H)+。
In the same synthesis method, diphenylcarbazole is replaced by the raw materials in table 3 to obtain the compounds with similar structures, as shown in table 3:
TABLE 3
Synthetic example 11: synthesis of formula 10
1.63g (5.0mmol, 1.0eq) of intermediate 2d, 1.84g (5.1mmol, 1.05eq) of 3-boronic acid-9, 9-spirofluorene, 0.09g (0.10mmol, 0.02eq) of tris (dibenzylideneacetone) dipalladium, 0.18g (0.40mmol, 0.08eq) of 2-dicyclohexylphosphonium-2, 4, 6-triisopropylbiphenyl, 2.1g (10.0mmol, 2.0eq) of potassium phosphate, 30ml of tetrahydrofuran and 5ml of deionized water were added, nitrogen was used for protection, and the reaction was carried out at 80 ℃ for 10 hours. The reaction was stopped, cooled to room temperature, poured into 100ml of water and extracted three times with dichloromethane. The organic phase was collected, dried over anhydrous sodium sulfate and the solvent removed by rotary evaporation. Dichloromethane/methanol recrystallization, filtration and drying gave 2.49g of a yellow solid in 82% yield, ms M/z 606.5(M + H) +.
In the same synthesis method, 3-boronic acid-9, 9-spirofluorene is replaced by the raw materials in table 4, so that the compounds with similar structures can be obtained, as shown in table 4.
TABLE 4
Synthetic example 22: synthesis of formula 11
1.85g (5.0mmol, 1.0eq) of intermediate 3d, 1.84g (5.1mmol, 1.05eq) of 2-boronic acid-9, 9-spirofluorene, 0.40g (0.40mmol, 0.04eq) of tetrakistriphenylphosphine palladium, 1.4g (10.0mmol, 2.0eq) of potassium carbonate were weighed, 20ml of toluene, 6ml of ethanol and 3ml of deionized water were added, nitrogen was used for protection, and reaction was carried out at 90 ℃ for 10 hours. The reaction was stopped, cooled to room temperature, poured into 100ml of water and extracted three times with dichloromethane. The organic phase was collected, dried over anhydrous sodium sulfate and the solvent removed by rotary evaporation. Recrystallization from dichloromethane/methanol, filtration and drying gave 2.73g of a yellow solid in 91% yield. The same synthesis method of mass spectrum M/z 606.5(M + H) + replacing 2-boronic acid-9, 9-spirofluorene with the raw material in table 5 can obtain the compound with similar structure, as shown in table 5.
TABLE 5
Synthetic example 32: synthesis of formula 66
1.85g (5.0mmol, 1.0eq) of intermediate 3d, 1.88g (5.5mmol, 1.10eq) of N- [1,1' -biphenyl-4-yl ] -9, 9-dimethyl-9H-fluoren-2-amine, 0.09g (0.1mmol, 0.02eq) of tris (dibenzylideneacetone) dipalladium, 0.15g (0.4mmol, 0.08eq) of tri-tert-butylphosphine, 3.26g (10.0mmol, 2.0eq) of cesium carbonate were weighed, 20ml of toluene was added, nitrogen blanketed, and reacted at 120 ℃ for 15H. The reaction was stopped, cooled to room temperature, poured into 100ml of water and extracted three times with dichloromethane. The organic phase was collected, dried over anhydrous sodium sulfate and the solvent removed by rotary evaporation. Silica gel column separation and vacuum drying gave 2.66g of a yellow solid in 82% yield, ms M/z 651.2(M + H) +.
In the same synthesis method, 2-boronic acid-9, 9-spirofluorene is replaced by the raw materials in table 6, so that the compounds with similar structures can be obtained, as shown in table 6.
TABLE 6
Synthetic example 37: synthesis of formula 69
1.80g (5.0mmol, 1.0eq) of intermediate 4c, 1.52g (10.5mmol, 2.10eq) of diphenylamine, 0.09g (0.1mmol, 0.02eq) of tris (dibenzylideneacetone) dipalladium, 0.18g (0.4mmol, 0.08eq) of 2-dicyclohexylphosphonium-2, 4, 6-triisopropylbiphenyl, 3.26g (10.0mmol, 2.0eq) of cesium carbonate were weighed, 30ml of toluene was added, nitrogen was used for protection, and reaction was carried out at 120 ℃ for 15 hours. The reaction was stopped, cooled to room temperature, poured into 100ml of water and extracted three times with dichloromethane. The organic phase was collected, dried over anhydrous sodium sulfate and the solvent removed by rotary evaporation. Silica gel column separation and vacuum drying gave 2.68g of yellow solid in 86% yield, mass M/z 626.4(M + H) +
In the same synthesis method, compounds with similar structures can be obtained by replacing diphenylamine with the raw materials shown in Table 7, as shown in Table 7.
TABLE 7
Synthetic example 40: synthesis of formula 77
1.80g (5.0mmol, 1.0eq) of intermediate 5c, 2.23g (10.5mmol, 2.10eq) of dibenzofuran-4-boronic acid, 0.09g (0.1mmol, 0.02eq) of tris (dibenzylideneacetone) dipalladium, 0.18g (0.4mmol, 0.08eq) of 2-dicyclohexylphosphonium-2, 4, 6-triisopropylbiphenyl, 3.26g (10.0mmol, 2.0eq) of cesium carbonate were weighed, 30ml of dioxane was added, nitrogen was used for protection, and reaction was carried out at 120 ℃ for 15 hours. The reaction was stopped, cooled to room temperature, poured into 100ml of water and extracted three times with dichloromethane. The organic phase was collected, dried over anhydrous sodium sulfate and the solvent removed by rotary evaporation. Silica gel column separation and vacuum drying gave 2.65g of a yellow solid in 85% yield, ms M/z 624.2(M + H) +.
In the same synthesis method, the dibenzofuran-4-boric acid is replaced by the raw materials in the table to obtain the compounds with similar structures, as shown in the table.
TABLE 8
The fluorescence emission rate constant of an organic molecule is largely determined by the degree of overlap of its highest occupied orbital (HOMO) and lowest unoccupied orbital (LUMO). For fluorescent molecules with donor-acceptor type structures, HOMO electron clouds are mainly distributed on donor units, such as arylamine and carbazole derivative structures in the invention, and LUMO electron clouds are mainly distributed on acceptor units, such as pyridine diphenoxy boron fluoride structures in the invention. The rate constant of fluorescence emission to the acceptor unit is therefore largely determined by the degree of conjugation to the acceptor unit. As shown in the figure, the REF-2 donor unit and the acceptor unit of the molecule in the literature (Angew. chem. int. Ed.2019,58, 9088-9094) are connected through a phenyl group, the HOMO and LUMO electron clouds are slightly overlapped, and the radiation rate is low; the 1-molecule of the invention connects the donor unit to the phenyl group of the acceptor unit, so that the HOMO and LUMO electron clouds have larger overlapping degree and higher fluorescence radiation rate constant. Therefore, when the molecular structure provided by the invention is used as a light-emitting object in an OLED device, the service life is longer.
As mentioned above, the TADF molecules are generally of donor/acceptor type, and the charge transfer in the molecule is enhanced by a nitrogen-containing strong donor unit such as aniline or carbazole to obtain a sufficiently small singlet-triplet energy level difference. As in the present invention, the acceptor unit of pyridine diphenoxyborofluoride is linked to the diphenylcarbazole donor unit to achieve TADF. As shown in FIG. 2, the fluorescence decay spectrum of the doped film of formula 2 obviously shows obvious two-component emission characteristics, which illustrates that formula 2 has TADF properties. However, nitrogen-containing strong donor units generally have good hole transport properties, and thus the existing TADF molecules exhibit mainly hole transport electrical properties. Research (adv. electron. mater.2019,5,1800708) shows that the electron transport property of the light-emitting layer in the OLED device has a greater influence on the service life of the device, but the molecular structure provided by the present invention can also realize effective thermally activated delayed fluorescence by connecting the receptor unit of pyridine diphenoxy boron fluoride with a non-nitrogen weak donor unit, such as dibenzofuran, dibenzothiophene, fluorene, phenanthrene, etc. As shown in FIG. 3, the fluorescence decay spectrum of the chemical-11 doped film obviously shows a remarkable two-component emission characteristic, which illustrates that the chemical-11 has TADF properties. The molecular structure without the strong hole transporting unit provides a TADF material with a predominant electron transporting property. Therefore, such TADF materials having a predominant electron transport property are also advantageous in improving the stability of the device.
The function of the film layer of the organic electroluminescent device according to the preferred embodiment of the present invention will be described below.
The organic electroluminescent device comprises an anode layer, a cathode layer and at least one organic layer between the anode and the cathode. Alternatively, the organic layer is a film layer formed by laminating a plurality of organic compounds. The organic layer may further contain an inorganic compound.
At least one layer of the organic layers of the organic electroluminescent device is a light-emitting layer. The organic layer may contain other functional layers in addition to the light-emitting layer, for example, one or more hole injection layers, hole transport layers, or electron blocking layers may be present between the anode layer and the light-emitting layer, an exciton blocking layer or an intermediate layer having a similar function may be present between the two light-emitting layers, and one or more hole blocking layers, electron transport layers, or electron injection layers may be present between the light-emitting layer and the cathode layer. Note that these functional layers are not necessarily present.
The organic electroluminescent device can be a fluorescent or phosphorescent device, and can also be a fluorescent and phosphorescent mixed device; the light emitting device may be a device having a single light emitting element or a tandem type device having a plurality of light emitting cells; further, the light emitting device may be a single color light emitting device, a mixed color light emitting device, or a white light emitting device.
The light emitting layer may include a plurality of guest materials and a plurality of host materials. The guest material may be a fluorescent material, a phosphorescent material, or a thermally activated delayed fluorescence material. The host material is a host material that occupies most of the components in the light-emitting layer, and the host material doped with a fluorescent material is referred to as a "fluorescent host" and the host material doped with a phosphorescent material is referred to as a "phosphorescent host". The host material is selected not depending on its molecular structure but depending on the host material as a guest material.
The compounds according to the invention according to the above embodiments can be used in different organic layers. Preferred are organic electroluminescent devices in which the compounds according to the invention are used as phosphorescent host materials, as light-emitting materials and/or in electron-transport layers and/or in hole-blocking layers. The use of the compounds of the invention of the above embodiments is equally applicable to organic electronic devices.
In a preferred embodiment of the present invention, the compound of the present invention is used as a phosphorescent host material in an organic electroluminescent device, and the light-emitting layer of the organic electroluminescent device described herein may be a single layer or a plurality of layers, wherein at least one layer contains the compound of the present invention.
In a preferred embodiment of the present invention, the compound of the present invention is used as a light-emitting material in an organic electroluminescent device, and one or more host materials may be selected and used in combination in a light-emitting layer of the organic electroluminescent device described herein.
In another preferred embodiment of the present invention, the compound of the present invention is used as a phosphorescent host material in an organic electroluminescent device, and one or more phosphorescent materials may be selected for use in combination with the host material in the light-emitting layer of the organic electroluminescent device described herein.
When the compound of the present invention is used as a host material, the compound of the present invention may be used singly or in combination of a plurality of host materials in the light-emitting layer of the organic electroluminescent device described herein. When a plurality of host materials are used together, at least one host material is the compound of the present invention, and other host materials may be other compounds of the present invention, or may be known host materials in the art or other disclosed or undisclosed host materials. The use mode can adopt a pre-mixing mode or a co-evaporation mode.
In a preferred embodiment of the present invention, the mixture doping ratio of the light emitting material and the host material in the light emitting layer of the organic electroluminescent device is preferably 0.1 wt% to 30 wt%.
In a further preferred embodiment of the present invention, the compounds according to the invention are used as electron transport layer materials in organic electroluminescent devices. The light-emitting material in the light-emitting layer in this embodiment may be a fluorescent material, a phosphorescent material, or a thermally activated delayed fluorescent material, or a mixture of a fluorescent material and a phosphorescent material in the light-emitting layer.
In this embodiment, the compound of the present invention is used in an electron transport layer, and may be doped with other electron transport materials. Other electron transport materials may be other compounds of the present invention, as well as electron transport materials known in the art or other disclosed or undisclosed electron transport materials. The use mode can adopt a pre-mixing mode or a co-evaporation mode.
In another preferred embodiment of the present invention, the compounds according to the invention are used as hole-blocking layer materials in organic electroluminescent devices. The light-emitting layer in this embodiment may be a fluorescent material, a phosphorescent material, or a thermally activated delayed fluorescent material, or a mixture of a fluorescent material and a phosphorescent material in the light-emitting layer.
In this embodiment, the compound of the present invention is used for a hole-blocking layer, and may be used by being doped with other hole-blocking layer materials. Other hole blocking layer materials may be other compounds of the present invention, as well as hole blocking layer materials known in the art or other disclosed or undisclosed hole blocking layer materials. The use mode can adopt a pre-mixing mode or a co-evaporation mode.
These methods are generally known to those skilled in the art and can be applied without inventive effort to organic electroluminescent devices comprising the compounds of the present invention.
The application effect of the compound in the organic electroluminescent device is explained in detail through device examples 1 to 33 and device comparative examples 1 to 17, and the technical progress and the beneficial effect of the compound in the field are verified. The examples and comparative examples are intended to illustrate the present invention in further detail, but the present invention is not limited to the technical conditions.
Device example 1: manufacture of organic electroluminescent device used as luminescent material of luminescent layer
A glass substrate with an Indium Tin Oxide (ITO) transparent electrode (anode) having a thickness of 25mm × 75mm × 1.1mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then subjected to Ultraviolet (UV) -ozone cleaning for 30 minutes. The thickness of the ITO film was 130 nm. The cleaned glass substrate was mounted on a substrate holder of a vacuum deposition apparatus, and the substrate holder was evacuated to 1X 10-5～1×10-6Pa, depositing a Hole Injection Layer (HIL) on the ITO transparent conductive layer, and the thickness is 15 nm. A hole transport layer A (HTL) was deposited on the hole injection layer to a thickness of 60 nm. Then, an Electron Blocking Layer (EBL) was deposited on the hole transport layer A to a thickness of 5 nm. Then, an emission layer (EML) was co-evaporated on the electron blocking layer to a film thickness of 20 nm. The luminescent layer (EML) adopts a multi-source co-evaporation mode to evaporate the luminescent material and the main material of the luminescent layer, wherein the doping concentration of the luminescent material is 5 weight percent. In order to ensure the accuracy of the doping concentration of the luminescent material, the shielding partition plate needs to be opened again after the evaporation rate of the luminescent material and the main body material is stable, and multi-source co-evaporation is carried out. Then, a Hole Blocking Layer (HBL) was deposited on the light-emitting layer to a thickness of 10 nm. Then, an Electron Transport Layer (ETL) was deposited on the hole-blocking layer to a thickness of 25 nm. Furthermore, inAn electron-injecting Electrode (EIL) 8-hydroxyquinoline lithium (Liq) was deposited on the ETL to a thickness of 1 nm. Then, metal cathode aluminum (Al) was deposited on the EIL to a film thickness of 80 nm. The structure of the organic electroluminescent device of example 1 is shown in fig. 1, and fig. 1 also shows the stacking sequence and the function of the functional layers.
TABLE 9 OLED materials
Device example 1:
ITO (130)/HATCN (15)/HTL-1(60)/EBL-1(10)/mCBP (8 (30, 5% by weight)/HBL-1 (10)/ETL-1: Liq (25, 50% by weight)/Liq (1)/Al (80).
Device examples 2 to 6 differ from device example 1 only in that the compound 8 of the present invention used in the light-emitting layer was replaced with another compound of the present invention, as specified in table 10.
Comparative examples 1 to 3:
comparative examples 1 to 3 are different from example 1 in that the light-emitting material of the light-emitting layer in the organic electroluminescent device was changed to REF-1 to REF-3 having similar structures reported in the industry, and the obtained device performance test data is shown in table 10.
The OLEDs were characterized by standard methods. For this purpose, the electroluminescence spectrum, the current efficiency (measured in cd/a), the power efficiency (measured in lm/W) and the external quantum efficiency (EQE, measured in%) are determined, which are calculated as a function of the luminous density from current/voltage/luminous density characteristic lines (IUL characteristic lines) which exhibit lambertian emission characteristics. At 1000cd/m2Determines the required voltage V1000 at the luminance of (c). CE1000 is expressed at 1000cd/m2The current efficiency achieved. Finally, EQE1000 is shown at 1000cd/m2External quantum efficiency at an operating luminance of (1), T95 denotes the device at 1000cd/m2The working time of the device for reducing the brightness to 95 percent under the initial brightnessT98 denotes the device is at 1000cd/m2The device luminance decreases to 98% of the on time at the initial luminance.
The device performances of examples 1 to 6 of the present invention and comparative examples 1 to 3 as light-emitting objects are summarized in table 10. It can be seen that the use of the material of the present invention can improve efficiency while maintaining a lower driving voltage, compared to the prior art (comparative examples 1 to 3). The EQE1000 in example 6 can reach 17.8%, and more importantly, the service life of the OLED is significantly improved, for example, T98 in example 6 can reach 48h, compared with the devices 1 to 3 in comparative examples, the service life is significantly improved.
Examples 7 to 14: manufacture of organic electroluminescent device used as phosphorescent host material of green light-emitting layer
Example 7: ITO (130)/HATCN (15)/HTL-1(60)/EBL-1 (10)/GD (30, 6% by weight)/HBL-1 (10)/ETL-1: Liq (25, 50% by weight)/Liq (1)/Al (80), and the number in parentheses indicates the film thickness (unit: nm).
Device examples 8 to 14 differ from device example 7 only in that the compound 3 of the present invention used in the light-emitting layer was replaced with another compound of the present invention, as specified in table 11.
TABLE 11
The device performances of examples 7 to 14 of the present invention and comparative examples 4 to 7 as green host GH are summarized in table 11. Host materials for phosphorescent OLED devices are generally the major component of the light-emitting layer, and studies have shown that balanced bipolar transport capabilities and small singlet-triplet energy level differences can be beneficial in suppressing the polaron-triplet interactions in the light-emitting layer, thereby improving device performance, particularly device lifetime (Organic Electronics 2018,5, 53-59). As can be seen from Table 11, the use of the material of the present invention can improve the efficiency while maintaining a low driving voltage, as compared with the prior art (comparative examples 4 to 7). Further, the electron-hole transport property can be further balanced by mixing the two host materials, the device lifetime is further improved (CN105579550), and the EQE1000 in example 8 is improved by 31.0% compared with comparative example 5 with a similar structure, and is also improved by 19.0% compared with the classical CBP (comparative example 7). More importantly, the service life of the OLED was significantly improved, such that T98 of example 9 was improved by 26.1% relative to the device of comparative example 7, while T98 of hybrid host device example 11 was improved by 53.3% relative to the device of comparative example 7.
Examples 15 to 22: manufacture of organic electroluminescent device used as phosphorescent host material of red light-emitting layer
Example 15: ITO (130)/HATCN (15)/HTL-1(60)/EBL-1 (10)/chemical formula 56: RD (30, 6% by weight)/HBL-1 (10)/ETL-1: Liq (25, 50% by weight)/Liq (1)/Al (80), and it should be noted that the number in parentheses indicates the film thickness (unit: nm).
Device examples 16 to 18 differ from device example 15 only in that the compound 56 of the present invention used in the light-emitting layer was replaced with another compound of the present invention, as specified in table 12.
Device examples 19 to 22 differed from device example 15 only in that the compound 56 of the present invention used in the light-emitting layer was replaced with a mixture (weight ratio 1:1) of another compound of the present invention and RH-2, as specified in table 12.
TABLE 12
The device performances of examples 15 to 22 of the present invention and comparative examples 8 to 11 as red light host RH are summarized in the table. As can be seen from table 12, compared to the prior art (comparative examples 8 to 11), the use of the material of the present invention can improve the efficiency while maintaining the lower driving voltage, as compared to comparative example 9 with similar structure, which is similar to EQE1000 in example 16, by approximately 17%. More importantly, the service life of the OLED is remarkably improved, such that T98 of example 17 is improved by 21.9% relative to the device of comparative example 10. Further, the electron hole transport properties can be further balanced by adopting a way of mixing two host materials, the device lifetime is further improved, and the T98 of the mixed host device example 22 is improved by 49.6% compared with the device of the comparative example 10.
Examples 23 to 28: manufacture of organic electroluminescent devices as hole blocking layer materials
Example 23: ITO (130)/HATCN (15)/HTL-1(60)/EBL-1(10)/CBP: GD (30, 6% by weight)/chemical (13) (10)/ETL-1: Liq (25, 50% by weight)/Liq (1)/Al (80), and it should be noted that the number in parentheses indicates the film thickness (unit: nm).
Device examples 24 to 28 differed from device example 23 only in that the compound 13 of the present invention used in the hole blocking layer was replaced with another compound of the present invention, which is specifically described in table 13.
Watch 13
Device properties of examples 23 to 28 of the present invention and comparative examples 12 to 14 as the hole blocking material HBL are summarized in table 13. It can be seen that, compared with the prior art (comparative examples 12 to 14), the efficiency can be improved while the driving voltage is kept low by using the material of the present invention, and the EQE1000 in example 26 is improved by 17.2% compared with comparative example 14. More importantly, the service life of the OLED is remarkably improved, such that T98 of example 27 is improved by 41.6% relative to the device of comparative example 14.
Examples 29 to 33: manufacture of organic electroluminescent devices as electron transport materials
Example 29: ITO (130)/HATCN (15)/HTL-1(60)/EBL-1(10)/CBP: GD (30, 6% by weight)/HBL-1 (10)/15: Liq (25, 50% by weight)/Liq (1)/Al (80), and the number in parentheses indicates the film thickness (unit: nm).
Device examples 30 to 33 differ from device example 29 only in that the compound 15 of the present invention used in the electron transport layer was replaced with another compound of the present invention, as specified in table 14.
TABLE 14
The device performance of examples 29 to 33 and comparative examples 15 to 17 of the present invention as the electron transport material ETL is summarized in table 14, and it can be seen that, compared with the prior art (comparative examples 15 to 17), the efficiency can be improved while the driving voltage is kept low by using the material of the present invention, and the EQE1000 in example 31 is improved by 14.8% compared with comparative example 17. More importantly, the service life of the OLED is remarkably improved, such as T98 of example 30 is improved by 36.9% relative to the device of comparative example 17.
Claims (10)
1. A pyridine diphenoxy boron fluoride compound, which has a structure shown by the combination of formula (1) and formula (2):
wherein,
the substituent represented by the formula (2) is only in R of the formula (1)2、R3、R9Or R10Position by a-and R2、R3、R9Or R10The positions are linked by keys;
in the formula (2), p and q are each independently an integer of 1 to 4;
in the formula (2), L is independently selected from a single bond, a substituted or unsubstituted straight chain or branched chain alkylene group with 1-20 carbon atoms, a substituted or unsubstituted cycloalkylene group with 3-20 ring carbon atoms, a substituted or unsubstituted arylene group with 6-30 ring carbon atoms, a substituted or unsubstituted heteroarylene group with 2-30 ring carbon atoms, a substituted or unsubstituted sub-condensed aryl ring with 10-50 ring carbon atoms, and a substituted or unsubstituted sub-condensed heterocyclic ring with 6-50 ring carbon atoms;
in the formula (2), X1～X8Are each independently selected from CR12Or N;
in the formula (2), Y1And Y2Are each independently selected from CR13R14、CR15CR16、SiR17R18、NR19O, S, wherein Y is2Can also be selected as single bond or hydrogen bond;
r of formula (1)1～R11R of the formula (2)12～R19The substituent groups are respectively and independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, a substituted amino group, a substituted silicon group, a substituted or unsubstituted alkyl group with 1-50 carbon atoms, a substituted or unsubstituted alkenyl group with 2-50 carbon atoms, a substituted or unsubstituted alkynyl group with 2-50 carbon atoms, a substituted or unsubstituted cycloalkyl group with 3-50 ring carbon atoms, a substituted or unsubstituted aryl group with 6-50 ring carbon atoms, or a substituted or unsubstituted 1-valent heterocyclic group with 5-50 ring carbon atoms;
adjacent R1～R19The substituent groups may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring, or may form a substituted or unsubstituted saturated or unsaturated fused ring with an adjacent aromatic or heteroaromatic ring.
2. The compound according to claim 1, the compound X in formula (2)1～X8The total number of nitrogen atoms in the nitrogen-containing compound is an integer of 0 to 5, preferably an integer of 0 to 3.
3. The compound according to claim 1 to 2, wherein the condensed ring group in formula (2) is preferably selected from the group consisting of:
4. the compound according to claim 1, wherein L in formula (2) is independently selected from any one or more of the following groups: pyridylene, phenylene, biphenylene, naphthylene, anthracenylene.
5. A compound according to claim 1, R1～R19The substituent groups are independently selected from any one or more of the following groups:
a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, a substituted amine group, a substituted silyl group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted indenofluorenyl group, a substituted or unsubstituted fluoranthryl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted perylene group, a substituted or unsubstituted amino group, a substituted or unsubstituted silyl group, a substituted
A substituted or unsubstituted tetracenyl group, a substituted or unsubstituted dibenzothiapyrrolyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzoselenophenyl group, a substituted or unsubstituted carbazolyl group.
6. The compound according to claim 1, wherein the term "substituted" in the compound referred to as "substituted or unsubstituted" means that the substituents are independently selected from deuterium atom, halogen atom, cyano group, nitro group, hydroxyl group, 1-valent arylamine group having 7 to 30 carbon atoms, 1-valent silicon group having 3 to 30 carbon atoms, 1-valent alkyl group or cycloalkyl group having 1 to 10 carbon atoms, 1-valent monocyclic aryl group or condensed ring aryl group having 6 to 30 carbon atoms, 1-valent heterocyclic group having 2 to 50 carbon atoms, or condensed ring heteroaryl group.
7. The compound of claim 1, wherein the compound is selected from the structures:
8. an organic electroluminescent element comprising an anode, a cathode and at least one organic thin film layer between the anode and the cathode, wherein the organic thin film layer contains the compound according to any one of claims 1 to 7.
9. The organic electroluminescent device according to claim 8, wherein the organic thin film comprises any one or a combination of at least two of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an exciton blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer, and the light emitting layer, the hole blocking layer and the electron transport layer comprise at least one layer of the compound according to any one of claims 1 to 8.
10. The organic electroluminescent device according to claim 8 or 9, wherein the compound is selected for use as a light-emitting material, a host material, a hole blocking material or an electron transport material of a light-emitting layer in the organic electroluminescent device.
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| CN115141173A (en) * | 2022-08-17 | 2022-10-04 | 浙江虹舞科技有限公司 | Compound and organic electroluminescent device comprising the same |
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| CN113105491B (en) | 2023-06-23 |
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