Organic electroluminescent compound, double-host-containing organic electroluminescent material, and organic electroluminescent device
By using specific heterocyclic combinations and deuteration technology, a dual-host organic electroluminescent material was formed, which solved the problems of low efficiency and short lifespan of existing phosphorescent materials, and realized organic electroluminescent devices with low driving voltage, high efficiency and long lifespan.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- JILIN OPTICAL & ELECTRONICS MATERIALS CO LTD
- Filing Date
- 2024-01-18
- Publication Date
- 2026-06-05
Smart Images
Figure CN117924205B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic electroluminescent materials, specifically relating to an organic electroluminescent compound containing a dual-host organic electroluminescent material and an organic electroluminescent device containing the same. Background Technology
[0002] Organic electroluminescence technology is the latest generation of flat panel display technology. Among organic light sources, phosphorescence has been highly regarded since its discovery because phosphorescent materials have significantly higher luminous efficiency than fluorescent materials, theoretically reaching 100% luminous efficiency. Therefore, many research institutions are increasing their R&D efforts on phosphorescent materials, attempting to accelerate industrialization through phosphorescent materials. For displays that require long-term use and high resolution, OLEDs with high luminous efficiency and / or long lifespan are needed.
[0003] However, existing phosphorescent materials used in organic light-emitting devices suffer from low efficiency and short lifetime. Therefore, how to provide an organic electroluminescent material with long lifetime, high efficiency, and low driving voltage is a problem that urgently needs to be solved by those skilled in the art. Summary of the Invention
[0004] In view of this, the present invention provides a dual-host organic electroluminescent material and an organic electroluminescent device containing the same. When the dual-host organic electroluminescent material of the present invention is applied to a specific light-emitting device, it has the advantages of low driving voltage, high luminous efficiency and long service life.
[0005] It should be noted that the present invention provides an organic electroluminescent device with a dual-body structure. The light-emitting device made by specific heterocyclic combinations and deuteration at specific positions not only significantly reduces the driving voltage, but also significantly improves the current efficiency and lifetime.
[0006] To achieve the above objectives, the present invention adopts the following technical solution:
[0007] The first technical objective of this invention is to provide an organic electroluminescent compound, which is represented by the following formula LA:
[0008]
[0009] in:
[0010] Both f and n are integers, and f + n = 1;
[0011] Ar1 is
[0012]
[0013] R4, R5, R6, R7, and R8 are all D;
[0014] Ar2 and Ar3 are independently selected from:
[0015]
[0016] R1, R2, R3, Ar4, Ar5, Ar6, and Ar7 are independently selected from C6-C30 aryl groups, C4-C20 heteroaryl groups, and combinations thereof; the aryl group is selected from substituted and unsubstituted benzene, naphthalene, anthracene, phenanthrene, biphenyl, terphenyl, tetraphenyl, fluorene, diphenylfluorene, and dibenzo[a]fluorene; the heteroaryl group is selected from substituted and unsubstituted pyridine, dibenzofuran, dibenzothiophene, quinoline, carbazole, benzonaphthofuran, benzonaphthothiophene, quinoxaline, quinazoline, benzo[a]carbazole, and dibenzo[a]carbazole; the substituent in the aryl and heteroaryl groups is D, F, or phenyl; when phenyl is substituted, the phenyl group can fuse with adjacent groups to form a ring.
[0017] Furthermore, the organic electroluminescent compound LA is selected from any of the following structures:
[0018]
[0019]
[0020]
[0021]
[0022]
[0023]
[0024]
[0025]
[0026]
[0027]
[0028]
[0029]
[0030]
[0031]
[0032]
[0033]
[0034]
[0035]
[0036]
[0037]
[0038]
[0039]
[0040]
[0041]
[0042]
[0043]
[0044]
[0045]
[0046]
[0047]
[0048]
[0049]
[0050]
[0051]
[0052]
[0053] The second technical objective of this invention is to provide a dual-host organic electroluminescent material, wherein the dual-host organic electroluminescent material comprises the organic electroluminescent compound LA and the organic electroluminescent compound LB as described above, and the mass ratio of LA to LB is 1:99-99:1.
[0054] The structural formula for LB is as follows:
[0055]
[0056] Wherein, La, Lb, Lc, X1, X2 and X3 are selected from single-bonded, substituted and unsubstituted C6-C30 aryl groups, substituted and unsubstituted C4-C20 heteroaryl groups, wherein the heteroatom in the heteroaryl group is O, S or N, and the substituents of the aryl and heteroaryl groups are D, F or phenyl.
[0057] Furthermore, the organic electroluminescent compound LB is selected from any of the following structures:
[0058]
[0059]
[0060]
[0061]
[0062]
[0063]
[0064]
[0065]
[0066]
[0067]
[0068]
[0069] The third technical objective of this invention is to provide an organic electroluminescent device.
[0070] The organic electroluminescent device includes a first electrode, a second electrode, and an organic electroluminescent material layer disposed between the first electrode and the second electrode; and the organic electroluminescent material layer includes a light-emitting layer; the light-emitting layer includes a doping material and a host material, and the host material includes the dual-host organic electroluminescent material as described above;
[0071] The mass ratio of the main material to the dopant material is 5-99.5:1.
[0072] As can be seen from the above technical solution, compared with the prior art, the present invention has the following beneficial effects:
[0073] The light-emitting device fabricated by this invention through specific heterocyclic combinations and deuteration at specific positions not only significantly reduces the driving voltage but also significantly improves current efficiency and lifetime; specifically,
[0074] 1. In this invention, by cationizing the phenyl hydrogen linked to the deuterated benzene in a specific heterocycle, the CH bond breaking is reduced, and the amorphous thin film formed after deuteration is better. The deuterated benzene linked to N forms a triarylamine host material, which has a better spatial structure than a triarylamine structure without N-type structure. The triarylamine host material has a better hole transport capability than a host structure containing a bistriarylamine structure. The driving voltage of the light-emitting device made with the N-type triarylamine structure is significantly reduced, and the current efficiency and lifetime are significantly improved.
[0075] 2. In this invention, the compounds formed by specific combinations of O and N heterocycles are more stable than those formed by combinations of S and N heterocycles. The driving voltage of the light-emitting devices made from the compounds of this invention is significantly reduced, and the current efficiency and lifetime are significantly improved.
[0076] 3. The first body LA of the present invention is combined with the second body LB containing a triazine structure to form the main body material. The first body LA has strong hole transport capability and the second body LB has strong electron transport capability. This results in higher hole and electron recombination efficiency in the light-emitting layer, which significantly reduces the driving voltage of the light-emitting device and significantly improves the current efficiency and lifetime. Attached Figure Description
[0077] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.
[0078] Figure 1 This is the mass spectrum of LA-002 in this invention.
[0079] Figure 2 This is the hydrogen nuclear magnetic resonance spectrum of the LA-002 of this invention.
[0080] Figure 3 This is the mass spectrum of LA-006 of the present invention.
[0081] Figure 4 This is the hydrogen nuclear magnetic resonance spectrum of LA-006 of the present invention.
[0082] Figure 5 This is the mass spectrum of LA-019 of the present invention.
[0083] Figure 6 This is the hydrogen nuclear magnetic resonance spectrum of LA-019 of the present invention.
[0084] Figure 7 This is the mass spectrum of the LA-020 of this invention.
[0085] Figure 8This is the hydrogen nuclear magnetic resonance spectrum of the LA-020 of this invention.
[0086] Figure 9 This is the mass spectrum of LA-021 of the present invention.
[0087] Figure 10 This is the 1H NMR spectrum of LA-021 of this invention.
[0088] Figure 11 This is the mass spectrum of LA-023 of the present invention.
[0089] Figure 12 This is the hydrogen nuclear magnetic resonance spectrum of LA-023 of the present invention. Detailed Implementation
[0090] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0091] This invention discloses a method for preparing a dual-host organic electroluminescent material.
[0092] Additionally, it should be noted that the values given in the following embodiments are as accurate as possible; however, those skilled in the art will understand that due to unavoidable measurement errors and experimental issues, each number should be understood as an approximation rather than an absolutely accurate value.
[0093] Example 1: Preparation of compound LA-002
[0094]
[0095] 1) Preparation of compound 1-1
[0096] Under nitrogen protection, 2-amino-6-bromophenol (compound A) (159.56 mmol) (CAS: 28165-50-6), benzaldehyde-D6 (191.47 mmol) (CAS: 17901-93-8), and sodium cyanide (159.56 mmol) (CAS: 143-33-9) were added sequentially to a 1000 ml three-necked reaction flask in 600 ml of N,N-dimethylformamide solvent. The reaction was carried out in an oil bath at 100 °C for 6 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, poured into water, extracted with ethyl acetate, concentrated the organic phase, and then purified by column chromatography to obtain compound 1-1 (26.0 g, yield 58.4%).
[0097] 2) Preparation of compound 1-2
[0098] Under nitrogen protection, compound 1-1 (82.39 mmol), 4-chloro-2-carboxyphenylboronic acid (90.76 mmol) (CAS: 913835-76-4), tetrakis(triphenylphosphine)palladium (3.28 mmol), and sodium carbonate (205.98 mmol) were added sequentially to a 1000 ml three-necked reaction flask in a mixed solvent of toluene (500 ml), EtOH (125 ml), and pure water (125 ml). The reaction was carried out in an oil bath at 140 °C for 5 hours, and a precipitate solid was formed. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and the precipitate solid product was washed with pure water and methanol to obtain compound 1-2 (19.5 g, yield 69.9%).
[0099] 3) Preparation of compounds 1-3
[0100] Under nitrogen protection, compounds 1-2 (47.23 mmol) and (methoxymethyl)triphenylphosphine chloride (70.89 mmol) (CAS: 4009-98-7) were dissolved in tetrahydrofuran (500 ml) solvent. The reaction mixture was stirred for 10 min, the reaction solution was cooled to 0 °C, potassium tert-butoxide was slowly added, and the mixture was stirred for 30 min after completion. The mixture was then heated to room temperature and stirred for another 3 hours. After the reaction was completed by TLC monitoring, pure water was added to the reaction solution to terminate the reaction. The reaction solution was extracted with ethyl acetate, and the extracted organic layer was dried with anhydrous magnesium sulfate. The solvent was removed by rotary evaporator, the organic phase was concentrated, and then purified by column chromatography to obtain compounds 1-3 (15.1 g, yield 87.1%).
[0101] 4) Preparation of compounds 1-4
[0102] Under nitrogen protection, compounds 1-3 (39.8 mmol) and Eaton reagent (1.4 ml) (CAS: 39394-84-8) were dissolved in chlorobenzene (200 ml) solvent and reacted in an oil bath at 80 °C for 3 hours. After the reaction was completed, the mixture was cooled to room temperature, the reaction solution was extracted with dichloromethane, the extracted organic layer was dried with anhydrous magnesium sulfate, the solvent was removed by rotary evaporator, the organic phase was concentrated, and then purified by column chromatography to obtain compounds 1-4 (10.6 g, yield 79.5%).
[0103] 5) Preparation of compound LA-002
[0104] Under nitrogen protection, compounds 1-4 (14.93 mmol), N-phenyl-4-benzidine (14.93 mmol) (CAS: 32228-99-2), tris(dibenzylacetone)palladium (0.75 mmol), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (1.493 mmol), and sodium tert-butoxide (30.0 mmol) were dissolved in o-xylene (100 ml) solvent and reacted in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and the product LA-002 (4.2 g, yield 51.7%) was obtained.
[0105] Mass spectrometry, such as Figure 1 As shown, the proton NMR spectrum is as follows: Figure 2 As shown.
[0106] Example 2: Preparation of compound LA-006
[0107]
[0108] 1) Preparation of compound 2-1
[0109] Under nitrogen protection, 3-bromoisoquinoline (144.19 mmol), (4-(phenylamino)phenyl)boronic acid (158.61 mmol) (CAS: 1228183-40-1), tetrakis(triphenylphosphine)palladium (5.74 mmol), and sodium carbonate (360.48 mmol) were added sequentially to a 1000 ml three-necked reaction flask in a mixed solvent of toluene (500 ml), EtOH (125 ml), and pure water (125 ml). The reaction was carried out in an oil bath at 140 °C for 6 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, poured into water, extracted with ethyl acetate, concentrated the organic phase, and then purified by column chromatography to obtain compound 2-1 (19.9 g, yield 66.3%).
[0110] 2) Preparation of compound LA-006
[0111] Under nitrogen protection, compounds 2-1 (59.74 mmol), 1-4 (59.74 mmol), tris(dibenzylacetone)dipalladium (3.0 mmol), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (5.974 mmol), and sodium tert-butoxide (120.0 mmol) were dissolved in o-xylene (100 ml) solvent. The reaction was carried out in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and the product LA-006 (20.1 g, yield 56.6%) was obtained.
[0112] Mass spectrometry, such as Figure 3 As shown, the proton NMR spectrum is as follows: Figure 4 As shown.
[0113] Example 3: Preparation of compound LA-019
[0114]
[0115] Under nitrogen protection, N-([[1,1'-biphenyl]-3-yl]dibenzo[B,D]thiophene-3-amine (59.74 mmol) (CAS: 1923735-65-2), compound 1-4 (59.74 mmol), tris(dibenzylacetone)dipalladium (3.0 mmol), 2-bicyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (5.974 mmol), and sodium tert-butoxide (120.0 mmol) were dissolved in o-xylene (100 ml) solvent. The reaction was carried out in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and the product LA-019 (23.6 g, yield 60.8%) was obtained. The mass spectra are as follows. Figure 5 As shown, the proton NMR spectrum is as follows: Figure 6 As shown.
[0116] Example 4: Preparation of compound LA-020
[0117]
[0118] Under nitrogen protection, N-([1,1'-biphenyl]-3-yl)dibenzo[b,d]furan-3-amine (59.74 mmol) (CAS: 1427556-46-3), compounds 1-4 (59.74 mmol), tris(dibenzylacetone)dipalladium (3.0 mmol), 2-bicyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (5.974 mmol), and sodium tert-butoxide (120.0 mmol) were dissolved in o-xylene (100 ml) solvent. The reaction was carried out in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and the product LA-020 (24.1 g, yield 63.7%) was obtained. Mass spectrometry is shown below. Figure 7 As shown, the proton NMR spectrum is as follows: Figure 8 As shown.
[0119] Example 5: Preparation of compound LA-021
[0120]
[0121] 1) Preparation of compound 3-1
[0122] Under nitrogen protection, 3-bromo-1.1':2',1"-terphenyl (64.68 mmol) (CAS: 1222633-95-5), 3-aminodibenzofuran (64.68 mmol) (CAS: 4106-66-5), tris(dibenzylacetone)palladium (1.3 mmol), tri-tert-butylphosphine (25.87 mmol), and sodium tert-butoxide (161.7 mmol) dissolved in toluene (500 ml) were added sequentially to a 500 ml three-necked reaction flask. The reaction was carried out in an oil bath at 60 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, poured into water, extracted with ethyl acetate, concentrated the organic phase, and then purified by column chromatography to obtain compound 3-1 (22.9 g, yield 86.0%).
[0123] 2) Preparation of compound LA-021
[0124] Under nitrogen protection, compounds 3-1 (48.60 mmol), 1-4 (48.60 mmol), tris(dibenzylacetone)dipalladium (2.4 mmol), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (0.486 mmol), and sodium tert-butoxide (97.6 mmol) were dissolved in o-xylene (100 ml) solvent. The reaction was carried out in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and the product LA-021 (17.5 g, yield 50.7%) was obtained.
[0125] Mass spectrometry, such as Figure 9 As shown, the proton NMR spectrum is as follows: Figure 10 As shown.
[0126] Example 6 Preparation of compound LA-023
[0127]
[0128] 1) Preparation of compound 4-4
[0129] Compound 4-4 is prepared in the same manner as compounds 1-4, except that 4-chloro-2-formylphenylboronic acid is replaced with 5-chloro-2-formylphenylboronic acid, while the other reactants are prepared in the same molar ratio.
[0130] 2) Preparation of compound LA-023
[0131] Under nitrogen protection, compound 4-4 (14.93 mmol), N-([1,1'-biphenyl]-3-yl)-[1,1':3',1'-triphenyl]-4-amine (14.93 mmol) (CAS: 1609484-77-6), tris(dibenzylacetone)dipalladium (0.75 mmol), 2-bicyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (1.493 mmol), and sodium tert-butoxide (30.0 mmol) were dissolved in o-xylene (100 ml) solvent. The reaction was carried out in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and yielded LA-023 product (6.7 g, yield 64.5%). Mass spectrometry: calculated value 695.88; measured value 695.82.
[0132] Mass spectrometry, such as Figure 11 As shown, the proton NMR spectrum is as follows: Figure 12 As shown.
[0133] Example 7 Preparation of compound LA-028
[0134]
[0135] The difference from Example 5 is that 3-bromo-1.1':2',1"-terphenyl was replaced with 4'-bromo-1,1':2',1"-terphenyl (CAS: 24253-40-5), compound 1-4 was replaced with 4-4, and other components and synthesis conditions remained unchanged, to obtain the LA-028 product (21.2 g, yield 61.4%).
[0136] Mass spectrometry: calculated value 709.86; measured value 709.88.
[0137] Example 8: Preparation of compound LA-029
[0138]
[0139] 1) Preparation of compound 6-1
[0140] Under nitrogen protection, 3-bromobenzo[B]naphtho[2,3-D]furan (64.68 mmol) (CAS: 1256544-32-7), 3-aminobiphenyl (64.68 mmol) (CAS: 2243-47-2), tris(dibenzylideneacetone)palladium (1.3 mmol), tri-tert-butylphosphine (25.87 mmol), and sodium tert-butoxide (161.7 mmol) dissolved in toluene (500 ml) were added sequentially to a 500 ml three-necked reaction flask. The reaction was carried out in an oil bath at 60 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, poured into water, extracted with ethyl acetate, concentrated the organic phase, and then purified by column chromatography to obtain compound 6-1 (16.8 g, yield 67.4%).
[0141] 2) Preparation of compound LA-029
[0142] Under nitrogen protection, compound 6-1 (48.60 mmol), compound 4-4 (48.60 mmol), tris(dibenzylacetone)dipalladium (2.4 mmol), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (0.486 mmol), and sodium tert-butoxide (97.6 mmol) were dissolved in o-xylene (100 ml) solvent. The reaction was carried out in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and the product LA-029 (17.5 g, yield 52.7%) was obtained.
[0143] Mass spectrometry: calculated value 683.82; measured value 683.81.
[0144] Example 9: Preparation of compound LA-031
[0145]
[0146] The difference from Example 8 is that 3-bromobenzo[B]naphtho[2,3-D]furan was replaced with 3-bromobenzo[B]naphtho[2,3-D]thiophene (CAS: 2189692-44-0), while the other components and synthesis conditions remained unchanged, to obtain the LA-031 product (16.9 g, yield 49.9%).
[0147] Mass spectrometry: calculated value 699.88; measured value 699.79.
[0148] Example 10: Preparation of compound LA-033
[0149]
[0150] Under nitrogen protection, N-(4-(-1-naphthyl)phenyl)-4-benzidine (59.74 mmol) (CAS: 897921-59-4), compound 4-4 (59.74 mmol), tris(dibenzylacetone)dipalladium (3.0 mmol), 2-bicyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (5.974 mmol), and sodium tert-butoxide (120.0 mmol) were dissolved in o-xylene (100 ml) solvent. The reaction was carried out in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and the product LA-033 (27.3 g, yield 68.2%) was obtained.
[0151] Mass spectrometry: calculated value 669.84; measured value 669.91.
[0152] Example 11 Preparation of compound LA-058
[0153]
[0154] 1) Preparation of compound 8-1
[0155] Under nitrogen protection, 9-(4-bromophenyl)carbazole (64.68 mmol) (CAS: 57102-42-8), 3-aminobiphenyl (64.68 mmol) (CAS: 2243-47-2), tris(dibenzylacetone)palladium (1.3 mmol), tri-tert-butylphosphine (25.87 mmol), and sodium tert-butoxide (161.7 mmol) dissolved in toluene (500 ml) were added sequentially to a 500 ml three-necked reaction flask. The reaction was carried out in an oil bath at 60 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, poured into water, extracted with ethyl acetate, and the organic phase was concentrated. Then, the solution was purified by column chromatography to obtain compound 8-1 (18.5 g, yield 69.7%).
[0156] 2) Preparation of compound LA-058
[0157] Under nitrogen protection, compound 8-1 (48.60 mmol), compound 1-4 (48.60 mmol), tris(dibenzylacetone)dipalladium (2.4 mmol), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (0.486 mmol), and sodium tert-butoxide (97.6 mmol) were dissolved in o-xylene (100 ml) solvent. The reaction was carried out in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and the product LA-058 (26.8 g, yield 77.8%) was obtained.
[0158] Mass spectrometry: calculated value 708.88; measured value 708.91.
[0159] Example 12 Preparation of compound LA-060
[0160]
[0161] 1) Preparation of compound 9-1
[0162] Under nitrogen protection, 2-(4-bromophenyl)pyridine (64.68 mmol) (CAS: 63996-36-1), 3-aminobiphenyl (64.68 mmol) (CAS: 2243-47-2), tris(dibenzylacetone)palladium (1.3 mmol), tri-tert-butylphosphine (25.87 mmol), and sodium tert-butoxide (161.7 mmol) dissolved in toluene (500 ml) were added sequentially to a 500 ml three-necked reaction flask. The reaction was carried out in an oil bath at 60 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, poured into water, extracted with ethyl acetate, concentrated the organic phase, and then purified by column chromatography to obtain compound 9-1 (17.1 g, yield 82.0%).
[0163] 2) Preparation of compound LA-060
[0164] Under nitrogen protection, compound 9-1 (48.60 mmol), compound 1-4 (48.60 mmol), tris(dibenzylacetone)dipalladium (2.4 mmol), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (0.486 mmol), and sodium tert-butoxide (97.6 mmol) were dissolved in o-xylene (100 ml) solvent. The reaction was carried out in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and the product LA-060 (26.3 g, yield 87.2%) was obtained.
[0165] Mass spectrometry: calculated value 620.77; measured value 620.73.
[0166] Example 13 Preparation of compound LA-079
[0167]
[0168] 1) Preparation of compound 10-1
[0169] Under nitrogen protection, 2-bromo-9-phenyl-9H-carbazole (64.68 mmol) (CAS: 94994-62-4), 3-aminobiphenyl (64.68 mmol) (CAS: 2243-47-2), tris(dibenzylacetone)palladium (1.3 mmol), tri-tert-butylphosphine (25.87 mmol), and sodium tert-butoxide (161.7 mmol) dissolved in toluene (500 ml) were added sequentially to a 500 ml three-necked reaction flask. The reaction was carried out in an oil bath at 60 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, poured into water, extracted with ethyl acetate, and the organic phase was concentrated. Then, the solution was purified by column chromatography to obtain compound 10-1 (18.2 g, yield 52.8%).
[0170] 2) Preparation of compound LA-079
[0171] Under nitrogen protection, compound 10-1 (48.60 mmol), compound 4-4 (48.60 mmol), tris(dibenzylacetone)dipalladium (2.4 mmol), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (0.486 mmol), and sodium tert-butoxide (97.6 mmol) were dissolved in o-xylene (100 ml) solvent. The reaction was carried out in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and the product LA-079 (27.1 g, yield 78.7%) was obtained.
[0172] Mass spectrometry: calculated value 708.88; measured value 708.92.
[0173] Example 14 Preparation of compound LA-081
[0174]
[0175] Under nitrogen protection, N-[1,1'-biphenyl-3-yl]-9,9-dimethyl-9H-fluorene-2-amine (59.74 mmol) (CAS: 1372778-66-9), compound 4-4 (59.74 mmol), tris(dibenzylacetone)dipalladium (3.0 mmol), 2-bicyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (5.974 mmol), and sodium tert-butoxide (120.0 mmol) were dissolved in o-xylene (100 ml) solvent. The reaction was carried out in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and the product LA-081 (31.3 g, yield 79.4%) was obtained. Mass spectrometry: calculated value 659.84; measured value 659.77.
[0176] Example 15 Preparation of compound LA-173
[0177]
[0178] 1) Preparation of compound 11-1
[0179] Under nitrogen protection, 4-bromodibenzothiophene (64.68 mmol) (CAS: 97511-05-2), o-aminobiphenyl (64.68 mmol) (CAS: 90-41-5), tris(dibenzylideneacetone)palladium (1.3 mmol), tri-tert-butylphosphine (25.87 mmol), and sodium tert-butoxide (161.7 mmol) dissolved in toluene (500 ml) were added sequentially to a 500 ml three-necked reaction flask. The reaction was carried out in an oil bath at 60 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, poured into water, extracted with ethyl acetate, concentrated the organic phase, and then purified by column chromatography to obtain compound 11-1 (14.9 g, yield 65.6%).
[0180] 2) Preparation of compound LA-173
[0181] Under nitrogen protection, compound 11-1 (48.60 mmol), compound 4-4 (48.60 mmol), tris(dibenzylacetone)dipalladium (2.4 mmol), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (0.486 mmol), and sodium tert-butoxide (97.6 mmol) were dissolved in o-xylene (100 ml) solvent. The reaction was carried out in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and LA-173 product (22.5 g, yield 71.2%) was obtained.
[0182] Mass spectrometry: calculated value 649.82; measured value 649.85.
[0183] Example 16 Preparation of compound LA-422
[0184]
[0185] Under nitrogen protection, 4-[N-(biphenyl-4-yl)-N-anilino]phenylboronic acid (71.69 mmol) (CAS: 1084334-86-0), compound 1-4 (59.74 mmol), tetrakis(triphenylphosphine)palladium (0.7 mmol), and potassium carbonate (215.1 mmol) were dissolved in a mixed solvent of toluene (500 ml), EtOH (125 ml), and pure water (125 ml). The reaction was carried out in an oil bath at 140 °C for 5 hours, and a precipitate solid was formed. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and the precipitate solid product was washed with pure water and methanol to obtain compound LA-422 (24.2 g, yield 65.4%).
[0186] Mass spectrometry: calculated value 619.78; measured value 619.85.
[0187] Example 17 Preparation of compound LA-443
[0188]
[0189] 1) Preparation of compounds 2-5
[0190] Under nitrogen protection, compound 4-4 (59.74 mmol), pinacol diborate (77.66 mmol), tris(dibenzylacetone)palladium (1.8 mmol), tricyclohexylphosphine (11.9 mmol), and potassium acetate (149.4 mmol) were dissolved in dioxane (200 ml) solvent and reacted in an oil bath at 110 °C for 5 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was then filtered to obtain compound 2-5 product (19.6 g, yield 77.0%).
[0191] 2) Preparation of compounds 2-6
[0192] Under nitrogen protection, compound 2-5 (33.28 mmol), m-chlorobromobenzene (30.25 mmol), tetrakis(triphenylphosphine)palladium (0.3 mmol), and potassium carbonate (90.7 mmol) were dissolved in a mixed solvent of toluene (400 ml), EtOH (100 ml), and pure water (100 ml). The mixture was reacted in an oil bath at 85 °C for 6 hours, and a precipitate of solid was formed. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and the precipitate was washed with pure water and methanol to obtain compound 2-6 (9.5 g, yield 76.4%).
[0193] 3) Preparation of compound LA-443
[0194] Under nitrogen protection, N-biphenyl-4-yl-3-dibenzo[B,D]furanamine (59.74 mmol) (CAS: 1290039-85-8), compound 2-6 (59.74 mmol), tris(dibenzylacetone)dipalladium (3.0 mmol), 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (5.974 mmol), and sodium tert-butoxide (120.0 mmol) were dissolved in o-xylene (100 ml) solvent. The reaction was carried out in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and the product LA-443 (28.1 g, yield 66.3%) was obtained.
[0195] Mass spectrometry: calculated value 709.86; measured value 709.85.
[0196] Example 18 Preparation of compound LA-444
[0197]
[0198] The difference from Example 17 is that N-biphenyl-4-yl-3-dibenzo[B,D]furanamine was replaced with N-[1,1'-biphenyl-4-yl]-9,9-dimethyl-9H-fluorene-2-amine (CAS: 897671-69-1), while the other components and synthesis conditions remained unchanged, yielding LA-444 product (31.3 g, yield 71.2%).
[0199] Mass spectrometry: calculated value 735.94; measured value 735.90.
[0200] Example 19 Preparation of compound LA-548
[0201]
[0202] 1) Preparation of compound 4-5
[0203] Under nitrogen protection, compound 4-4 (59.74 mmol), pinacol diborate (77.66 mmol), tris(dibenzylacetone)palladium (1.8 mmol), tricyclohexylphosphine (11.9 mmol), and potassium acetate (149.4 mmol) were dissolved in dioxane (200 ml) solvent and reacted in an oil bath at 110 °C for 5 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and compound 4-5 product (16.2 g, yield 63.6%) was obtained.
[0204] 2) Preparation of compounds 4-6
[0205] Under nitrogen protection, compounds 4-5 (33.28 mmol), 1-chloro-4-bromonaphthalene (30.25 mmol), tetrakis(triphenylphosphine)palladium (0.3 mmol), and potassium carbonate (90.7 mmol) were dissolved in a mixed solvent of toluene (400 ml), EtOH (100 ml), and pure water (100 ml). The mixture was reacted in an oil bath at 85 °C for 6 hours, during which a precipitate of solid was formed. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and the precipitate was washed with pure water and methanol to obtain compound 4-6 (10.6 g, yield 76.0%).
[0206] 3) Preparation of compound LA-548
[0207] Under nitrogen protection, N-[1,1'-biphenyl]-3-yl-[1,1'-biphenyl]-4-amine (59.74 mmol) (CAS: 570391-47-8), compound 4-6 (59.74 mmol), tris(dibenzylacetone)dipalladium (3.0 mmol), 2-bicyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (5.974 mmol), and sodium tert-butoxide (120.0 mmol) were dissolved in o-xylene (100 ml) solvent. The reaction was carried out in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and the product LA-548 (30.7 g, yield 68.9%) was obtained.
[0208] Mass spectrometry: calculated value 745.94; measured value 745.87.
[0209] Example 20: Preparation of compound LA-590
[0210]
[0211] The difference from Example 19 is that N-[1,1'-biphenyl]-3-yl-[1,1'-biphenyl]-4-amine was replaced with N-(4-biphenyl)dibenzo[b,d]thiophene-3-amine (CAS: 1290039-87-0), while the other components and synthesis conditions remained unchanged, yielding the LA-590 product (33.9 g, yield 72.5%).
[0212] Mass spectrometry: calculated value 775.98; measured value 775.93.
[0213] Example 21 Preparation of compound LA-157
[0214]
[0215] The difference from Example 4 is that compounds 1-4 were replaced with 4-4, while other components and synthesis conditions remained unchanged, yielding the LA-157 product (25.6 g, yield 67.6%).
[0216] Mass spectrometry: calculated value 633.76; measured value 633.79.
[0217] Example 22 Preparation of compound LA-169
[0218]
[0219] The difference from Example 22 is that N-([1,1'-biphenyl]-3-yl)dibenzo[b,d]furan-3-amine was replaced with N-([[1,1'-biphenyl]-3-yl]dibenzo[B,D]thiophene-3-amine (CAS: 1923735-65-2), while the other components and synthesis conditions remained unchanged, yielding the LA-169 product (21.9 g, yield 56.4%).
[0220] Mass spectrometry: calculated value 649.82; measured value 649.80.
[0221] Example 23 Preparation of compound LA-182
[0222]
[0223] 1) Preparation of compound 13-1
[0224] Under nitrogen protection, 2-bromodibenzofuran (64.68 mmol) (CAS: 86-76-0), 3,4-diphenylaniline (64.68 mmol) (CAS: 10569-67-2), tris(dibenzylacetone)palladium (1.3 mmol), tri-tert-butylphosphine (25.87 mmol), and sodium tert-butoxide (161.7 mmol) dissolved in toluene (500 ml) were added sequentially to a 500 ml three-necked reaction flask. The reaction was carried out in an oil bath at 60 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, poured into water, extracted with ethyl acetate, concentrated the organic phase, and then purified by column chromatography to obtain compound 13-1 (15.9 g, yield 59.7%).
[0225] 2) Preparation of compound LA-182
[0226] Under nitrogen protection, compound 13-1 (48.60 mmol), compound 4-4 (48.60 mmol), tris(dibenzylacetone)dipalladium (2.4 mmol), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (0.486 mmol), and sodium tert-butoxide (97.6 mmol) were dissolved in o-xylene (100 ml) solvent. The reaction was carried out in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and the product LA-182 (19.5 g, yield 56.5%) was obtained.
[0227] Mass spectrometry: calculated value 709.86; measured value 709.88.
[0228] Example 24 Preparation of compound LA-232
[0229]
[0230] The difference from Example 22 is that N-([1,1'-biphenyl]-3-yl)dibenzo[b,d]furan-3-amine was replaced with 3,6-diphenyl-9H-carbazole (CAS: 56525-79-2), while the other components and synthesis conditions remained unchanged, to obtain the LA-232 product (27.5 g, yield 74.5%).
[0231] Mass spectrometry: calculated value 617.76; measured value 617.71.
[0232] Example 25 Preparation of compound LA-259
[0233]
[0234] 1) Preparation of compound 14-1
[0235] Under nitrogen protection, dibenzofuran-2-boronic acid (71.69 mmol) (CAS: 402936-15-6), 3-bromo-6-phenyl-9H-carbazole (59.74 mmol) (CAS: 1303472-72-1), tetra-triphenylphosphine-palladium (0.7 mmol), and potassium carbonate (215.1 mmol) were dissolved in a mixed solvent of toluene (500 ml), EtOH (125 ml), and pure water (125 ml). The reaction was carried out in an oil bath at 140 °C for 5 hours, and a precipitate solid was formed. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and the precipitate solid product was washed with pure water and methanol to obtain compound 14-1 (19.1 g, yield 78.1%).
[0236] 2) Preparation of compound LA-259
[0237] Under nitrogen protection, compound 14-1 (48.60 mmol), compound 1-4 (48.60 mmol), tris(dibenzylacetone)dipalladium (2.4 mmol), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (0.486 mmol), and sodium tert-butoxide (97.6 mmol) were dissolved in o-xylene (100 ml) solvent. The reaction was carried out in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and the product LA-259 (22.6 g, yield 65.7%) was obtained.
[0238] Mass spectrometry: calculated value 707.74; measured value 707.83.
[0239] Example 26 Preparation of compound LA-486
[0240]
[0241] 1) Preparation of compound 15-1
[0242] Under nitrogen protection, compound 2-5 (33.28 mmol), p-chlorobromobenzene (30.25 mmol), tetrakis(triphenylphosphine)palladium (0.3 mmol), and potassium carbonate (90.7 mmol) were dissolved in a mixed solvent of toluene (400 ml), EtOH (100 ml), and pure water (100 ml). The reaction was carried out in an oil bath at 85 °C for 6 hours, and a precipitate solid was formed. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and the precipitate solid product was washed with pure water and methanol to obtain compound 15-1 (9.8 g, yield 78.8%).
[0243] 2) Preparation of compound LA-486
[0244] Under nitrogen protection, N-phenyl-4-benzidine (59.74 mmol) (CAS: 32228-99-2), compound 15-1 (59.74 mmol), tris(dibenzylacetone)dipalladium (3.0 mmol), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (5.974 mmol), and sodium tert-butoxide (120.0 mmol) were dissolved in o-xylene (100 ml) solvent and reacted in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and the product LA-486 (24.9 g, yield 67.2%) was obtained.
[0245] Mass spectrometry: calculated value 619.78; measured value 619.66.
[0246] Example 27 Preparation of compound LA-503
[0247]
[0248] The difference from Example 27 is that N-phenyl-4-benzidine was replaced with N-phenyl-3-dibenzofuran-2-amine (CAS: 406488-21-9), while the other components and synthesis conditions remained unchanged, to obtain the LA-503 product (25.2 g, yield 66.5%).
[0249] Mass spectrometry: calculated value 633.76; measured value 633.71.
[0250] Example 28 Preparation of compound LA-555
[0251]
[0252] 1) Preparation of compound 12-1
[0253] Under nitrogen protection, N-(3-bromophenyl)-N-phenyl-[1,1-biphenyl]-4-amine (64.68 mmol) (CAS: 1134188-19-4), aniline (64.68 mmol), tris(dibenzylacetone)dipalladium (1.3 mmol), tri-tert-butylphosphine (25.87 mmol), and sodium tert-butoxide (161.7 mmol) were added sequentially to a 500 ml three-necked reaction flask in toluene (500 ml) solvent. The reaction was carried out in an oil bath at 60 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, poured into water, extracted with ethyl acetate, concentrated the organic phase, and then purified by column chromatography to obtain compound 12-1 (24.1 g, yield 90%).
[0254] 2) Preparation of compound LA-555
[0255] Under nitrogen protection, compound 12-1 (48.60 mmol), compound 4-4 (48.60 mmol), tris(dibenzylacetone)dipalladium (2.4 mmol), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (0.486 mmol), and sodium tert-butoxide (97.6 mmol) were dissolved in o-xylene (100 ml) solvent. The reaction was carried out in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and the product LA-555 (30.3 g, yield 88%) was obtained.
[0256] Example 29 Preparation of compound LA-556
[0257]
[0258] 1) Preparation of compound 16-1
[0259] Under nitrogen protection, 3-bromo-N,N-diphenylaniline (64.68 mmol) (CAS: 78600-33-6), aniline (64.68 mmol), tris(dibenzylacetone)palladium (1.3 mmol), tri-tert-butylphosphine (25.87 mmol), and sodium tert-butoxide (161.7 mmol) dissolved in toluene (500 ml) were added sequentially to a 500 ml three-necked reaction flask. The reaction was carried out in an oil bath at 60 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, poured into water, extracted with ethyl acetate, concentrated the organic phase, and then purified by column chromatography to obtain compound 12-1 (24.1 g, yield 75%).
[0260] 2) Preparation of compound LA-556
[0261] Under nitrogen protection, compound 16-1 (48.60 mmol), compound 4-4 (48.60 mmol), tris(dibenzylacetone)palladium (2.4 mmol), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (0.486 mmol), and sodium tert-butoxide (97.6 mmol) were dissolved in o-xylene (100 ml) solvent. The reaction was carried out in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and the product LA-556 (21.3.3 g, yield 69%) was obtained.
[0262] Example 30: Preparation of compound LA-607
[0263]
[0264] Under nitrogen protection, N-phenyl-3-dibenzofuran-2-amine (59.74 mmol) (CAS: 406488-21-9), compound 4-6 (59.74 mmol), tris(dibenzylacetone)palladium (3.0 mmol), 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl (s-phos) (5.974 mmol), and sodium tert-butoxide (120.0 mmol) were dissolved in o-xylene (100 ml) solvent. The reaction was carried out in an oil bath at 170 °C for 3 hours. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and then the reaction solution was added dropwise to methanol to precipitate a solid. The solid was obtained by filtration and the product LA-607 (30.3 g, yield 74.2%) was obtained.
[0265] Mass spectrometry: calculated value 683.82; measured value 683.87.
[0266] Device Example 1
[0267] Organic electroluminescent devices were prepared using compounds LA-002 and LB-001 prepared in Example 1 above. The specific steps are as follows:
[0268] 1) Substrate processing:
[0269] Select ITO / Ag / ITO glass with anodized surface as substrate. First, use stripping solution to remove the protective film on the substrate surface. Then, use deionized water to perform ultrasonic and spray processes on the substrate after film removal. Finally, bake the substrate.
[0270] 2) Evaporation process:
[0271] ① After cleaning, a glass substrate is selected, and a hole injection material HI-01 is deposited on the substrate with an anode using vacuum evaporation to form a thickness of [thickness missing]. The hole injection layer is composed of HT-01 and HI-01 co-evaporated, with HI-01 doping ratio of 3%.
[0272] ② Hole transport material HT-01 is deposited on the hole injection layer by vacuum evaporation to form a thickness The hole transport layer.
[0273] ③ The light-emitting host material (LA-002:LB-001 = 1:1) and the dopant material RD-01 are mixed and deposited on the hole transport layer by vacuum evaporation at a mass ratio of 97:3 to form a layer with a thickness of [missing information]. The luminescent layer.
[0274] ④ A hole blocking layer material HB-01 is deposited on the light-emitting layer by vacuum evaporation to form a thickness of Hole-blocking layer.
[0275] ⑤ Electron transport materials ET-01 and Liq are mixed and deposited in a 50:50 mass ratio on the hole blocking layer by vacuum evaporation to form a layer with a thickness of [missing information]. The electron transport layer.
[0276] ⑥ Electron injection material YB is deposited on the electron transport layer by vacuum evaporation to form a layer with a thickness of [missing information]. The electron injection layer.
[0277] ⑦ A cathode material Mg:Ag (1:9) is deposited on the electron injection layer by vacuum evaporation to form a layer with a thickness of [missing information]. The cathode.
[0278] ⑧ CP-01 material is deposited on the cathode by vacuum evaporation to form a thickness of [missing information]. By extracting the light from the layer, a light-emitting device can be obtained.
[0279] Other device embodiments and comparative examples are similar to device embodiment 1, except for the main material and doping material of the light-emitting layer. The manufacturing methods are the same as those of device embodiment 1, and will not be described in detail here. They are shown in Table 1.
[0280] Table 1. Light-emitting layer materials for each device embodiment and device comparison example.
[0281]
[0282]
[0283] The structure of the device is as follows:
[0284]
[0285]
[0286]
[0287]
[0288] Table 2. Detection results of light-emitting devices in Device Examples 1-30 and Device Comparative Examples 1-47.
[0289]
[0290]
[0291]
[0292] In summary, as shown in Table 2, the light-emitting devices made using the specific heterocyclic combination and deuteration at specific positions provided in this application exhibit significantly reduced driving voltage and significantly improved current efficiency and lifetime. Specifically:
[0293] 1. In this invention, by cationizing the phenyl hydrogen linked in a specific heterocycle after deuteration, the CH bond breaking is reduced, and the amorphous thin film formed after deuteration is better. At the same time, compared with the device examples 1-29 and the device comparative examples 1-29, the light-emitting device made of the compound of this invention after deuteration of benzene has a significantly lower driving voltage, and a significantly improved current efficiency and lifetime.
[0294] 2. In this invention, the compounds formed by specific combinations of O and N heterocycles are more stable than those formed by combinations of S and N heterocycles. Furthermore, compared with device example 7 and device comparative example 30, the light-emitting devices made from the compounds of this invention have significantly lower driving voltages, and significantly improved current efficiency and lifetime.
[0295] 3. In this invention, a triarylamine host material is formed by specific heterocyclic and deuteration followed by connection with N. Compared with triarylamine structures without N-type structures, the hole transport capability is better. At the same time, compared with device embodiment 7 and device comparisons 31-35, the driving voltage of the light-emitting device made with N-type triarylamine structure is significantly reduced, and the current efficiency and lifetime are significantly improved.
[0296] 4. In this invention, only deuteration of the benzene ring connected by specific O and N heterocycles results in a more stable compound with a stronger ability to transport holes and electrons. Furthermore, compared with device examples 1, 6, 30 and device comparisons 36, 37, 38, 39, 46, 47, the light-emitting devices made from compounds deuterated on the benzene ring have significantly lower driving voltages, and significantly improved current efficiency and lifetimes compared to compounds deuterated at other positions.
[0297] 5. The first main body of the present invention is combined with a second main body containing a triazine structure to form a main body material. The first main body has strong hole transport capability and the second main body has strong electron transport capability. This results in higher hole and electron recombination efficiency in the light-emitting layer. At the same time, compared with device examples 1, 6, 11, 17, 14, 25 and device pairs 40-45, the light-emitting device made with the second main body compound provided by the present invention has a significantly lower driving voltage, and a significantly improved current efficiency and lifetime compared with compounds that do not contain triazine groups.
[0298] 6. In this invention, partial deuteration can improve the current efficiency and lifetime of the device. As seen in Device Example 30 and Comparative Example 47, deuteration is generally considered to improve efficiency and extend lifetime, with the mechanism presumably being that deuterium (D) has lower activity than hydrogen (H). However, chemical reactivity does not completely correspond to the activity under OLED electroluminescence conditions. For example, data from the embodiments of prior art patent CN112812106B demonstrate that in the green light host material shown there, the deuteration of the compound does not have an ideal impact on the device's efficiency and lifetime. Therefore, strictly speaking, the effect of deuteration or partial deuteration on the performance of OLED materials does not provide a definite directional guideline, and the current efficiency of the partially deuterated device in Device Example 30 of this invention is significantly higher than that of the device in Comparative Example 47.
[0299] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims
1. An organic electroluminescent compound, characterized in that, The organic electroluminescent compound is represented by the following formula LA: ； in: Both f and n are integers, and f + n = 1; Ar1 is ； R4, R5, R6, R7, and R8 are all D; Ar2 and Ar3 are independently selected from: ， R1, R2, R3, Ar4, Ar5, Ar6, and Ar7 are independently selected from C6-C30 aryl groups and C4-C20 heteroaryl groups; the aryl group is selected from substituted and unsubstituted benzene, naphthalene, anthracene, phenanthrene, biphenyl, terphenyl, tetraphenyl, fluorene, diphenylfluorene, and dibenzo[a]fluorene; the heteroaryl group is selected from substituted and unsubstituted pyridine, dibenzofuran, dibenzothiophene, quinoline, carbazole, benzonaphthofuran, benzonaphthothiophene, quinoxaline, quinazoline, benzo[a]carbazole, and dibenzo[a]carbazole; the substituent in the aryl and heteroaryl groups is D, F, or phenyl; when phenyl is substituted, the phenyl group can fuse with adjacent groups to form a ring.
2. The organic electroluminescent compound according to claim 1, characterized in that, The organic electroluminescent compound LA is selected from any one of the following structures: ; ； 。 3. A dual-host organic electroluminescent material, characterized in that, The dual-host organic electroluminescent material comprises the organic electroluminescent compound LA and the organic electroluminescent compound LB as described in claim 1, wherein the mass ratio of LA to LB is 1:99-99:1, and the structural formula of LB is as follows: ； Wherein, La, Lb, and Lc are selected from single bonds, and X1, X2, and X3 are independently selected from substituted and unsubstituted C6-C30 aryl groups and substituted and unsubstituted C4-C20 heteroaryl groups, respectively. The heteroatoms in the heteroaryl group are O, S, or N, and the substituents of the aryl and heteroaryl groups are D, F, or phenyl.
4. The dual-host organic electroluminescent material according to claim 3, characterized in that, The organic electroluminescent compound LB is selected from any of the following structures: .
5. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes a first electrode, a second electrode, and an organic electroluminescent material layer disposed between the first electrode and the second electrode; and the organic electroluminescent material layer includes a light-emitting layer; the light-emitting layer includes a doping material and a host material, and the host material includes the organic electroluminescent material with dual host as described in claim 3.
6. The organic electroluminescent device according to claim 5, characterized in that, The mass ratio of the main material to the dopant material is 5-99.5:1.