Boron-containing multiple resonance type thermal activation delayed fluorescence material and organic electroluminescent device thereof

Abstract

The invention relates to the technical field of organic electroluminescent materials, in particular to a boron-containing multiple resonance type thermal activation delayed fluorescence material and an organic electroluminescent device thereof. The boron-containing multi-resonance type thermal activation delayed fluorescence material provided by the invention has the core of a spirofluorene locking strategy, and compared with the prior art, the boron-containing multi-resonance type thermal activation delayed fluorescence material has the advantages that firstly, a spirofluorene unit is covalently connected with a B / N doped multi-resonance core through a rigid spirofluorene bridge, and a pi conjugated system is expanded on the premise of not damaging an MR resonance structure, so that red shift of emission is realized; secondly, due to the three-dimensional space steric effect of the spiro-carbon unit, on one hand, molecular vibration and conformational change are limited, relaxation of an excited state structure is inhibited, and a narrow spectrum is maintained; on the other hand, pi-pi accumulation among molecules is hindered, aggregation-induced quenching is effectively inhibited, and wide doping concentration stability is achieved; and the spiro carbon bridge enhances the molecular planarity and rigidity, improves the thermal stability of the material, and improves the stability of the device.

Description

Technical Field

[0001] This invention relates to the field of organic electroluminescent materials technology, and in particular to a boron-containing multiple resonance thermally activated delayed fluorescence material and its organic electroluminescent device. Background Technology

[0002] OLED technology, with its advantages of self-emission, high contrast, wide viewing angle, and flexibility, has become the mainstream technology for display products such as smartphones, televisions, and AR / VR devices. To achieve display devices that comply with the BT.2020 ultra-high-definition color standard set by the International Telecommunication Union (ITU-R), narrow-spectrum, high-color-purity red, green, and blue primary color emitting materials are required. Traditional fluorescent, phosphorescent, and thermally activated delayed fluorescence (TADF) materials have significant drawbacks: fluorescent materials typically have a full width at half maximum (FWHM) greater than 50 nm; phosphorescent materials rely on noble metals (such as Ir and Pt), resulting in high costs and significant spectral broadening; and traditional TADF materials, due to significant relaxation in the excited-state structure, have FWHMs mostly between 70 and 100 nm, all of which fail to meet the BT.2020 standard's requirements for green light.

[0003] The multiple resonance (MR) strategy proposed in 2016 achieved narrow-spectrum emission (FWHM < 25 nm) by constructing a rigid B / N-doped fused-ring aromatic framework to restrict excited-state structural relaxation, thus providing a possibility for BT.2020 compatible materials. While some progress has been made in reported MR luminescent materials, existing boron-containing multiple resonance TADF materials, although attempting to address the color purity issue, have not formed an effective structural locking mechanism, failing to simultaneously achieve synergistic optimization of wide doping stability, high color purity, and long lifetime. Therefore, developing MR-TADF materials that combine high color purity, wide doping stability, high efficiency, and long lifetime is crucial for promoting the industrialization of ultra-high-definition OLED technology.

[0004] Therefore, existing technologies still need improvement and development. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the present invention provides a boron-containing multiple resonance thermally activated delayed fluorescence material and an organic electroluminescent device thereof. The compound of the present invention can be used as a doping material for the light-emitting layer of an organic electroluminescent device.

[0006] To achieve this objective, the present invention adopts the following technical solution: In a first aspect, the present invention provides a boron-containing multiple resonance thermally activated delayed fluorescence material, the molecular structure of which is shown in general formula (I) and general formula (II): ; In general formulas (I) and (II): Rings A, B, C, and D are independently represented as substituted or unsubstituted C6-C6 groups. 30 Aromatic rings, substituted or unsubstituted C5-C 30 One of the aromatic rings; Ring A and ring B, and ring C and ring D are not connected, or are connected by a single CC bond; R1-R 10 Each time it appears, the same or different representations are hydrogen atom, deuterium atom, tritium atom, halogen atom, cyano group, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkenyl, substituted or unsubstituted C1-C 10 Alkynyl, substituted or unsubstituted silyl, substituted or unsubstituted boryl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C6-C 30 Aryloxy group, substituted or unsubstituted aromatic amino group, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C5-C 30 One of the heteroaryl groups; R1-R 10 Any two adjacent elements in the loop can either form a loop or remain unconnected; X1 and X2 are independently represented as NR. 11 One of O, S, and Se; R 11 Indicated as substituted or unsubstituted C1~C 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted aromatic amino groups, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C5-C 30 One of the heteroaryl groups; Substituents replacing the aforementioned substituents independently represent substituents from monosubstituted groups to the maximum permissible number of substitutions, optionally selected from deuterium, tritium, halogen, cyano, trifluoromethyl, C1-C 40 Alkyl, C1-C 40 Alkoxy, C1-C 40 Alkylthio, C3-C 40 Cycloalkyl, substituted or unsubstituted aromatic amino, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C4-C 60 Mixed aromatics; The heteroatom in the heteroaryl group is selected from one or more of N, O, S, Se, Te, or B.

[0007] Preferably, rings A, B, C, and D are independently represented as substituted or unsubstituted C6-C6 groups. 20 Aromatic rings, substituted or unsubstituted C5-C 20 One of the aromatic rings.

[0008] Preferably, the R1-R 10 The group is independently selected from hydrogen, deuterium, tritium, halogen atom, cyano, trifluoromethyl, or substituted or unsubstituted of the following groups: silyl, amino, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, phenyl, methylphenyl, isopropylphenyl, tert-butylphenyl, phenolyl, thiophenolyl, selenophenolyl, aniline, naphthyl, anthraceneyl, phenanthrene, pyrene, tetraphenyl, fluorenyl, 9,9-dimethylfluorenyl, 9 One of 9-diphenylfluorenyl, spirodifluorenyl, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indyl, furanyl, benzofuranyl, thiophene, benzothiophene, pyrroleyl, isoindolyl, carbazolyl, pyridinyl, quinolinyl, isoquinolinyl, acridineyl, phenanthridineyl, pyrazolyl, imidazolyl, 1,2-thiazolyl, 1,3-thiazolyl, pyridazinyl, pyrimidinyl, quinoxalinyl, pyrazinyl, phenazinyl, phenothiazinyl, azacarbazolyl, 1,3,5-triazinyl, dimilboryl, di(2,4,6-triisopropylphenyl)boryl, or a combination of the above two groups.

[0009] Preferably, the boron-containing multiple resonance delayed fluorescence material is any one of the following compounds: ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; .

[0010] The present invention also provides an organic electroluminescent device having an anode, a cathode, and an organic layer, wherein the organic layer includes a light-emitting layer, and the light-emitting side includes the aforementioned boron-containing multiple resonance thermally activated delayed fluorescence material.

[0011] The beneficial effects of this invention are as follows: The boron-containing multi-resonance thermally activated delayed fluorescence material provided by this invention is based on the "spirofluorene locking strategy". Compared with the prior art, (1) the helical carbon unit is covalently connected to the B / N doped multi-resonance core through a rigid helical carbon bridge, which expands the π-conjugated system without destroying the MR resonance structure, thus redshifting the emission; (2) the three-dimensional spatial steric hindrance effect of the helical carbon unit restricts molecular vibration and conformational changes, suppresses excited state structural relaxation, and maintains a narrow spectrum; on the other hand, it hinders the π-π stacking between molecules, effectively suppresses aggregation-induced quenching (ACQ), and achieves stability across wide doping concentrations; (3) the helical carbon bridge enhances molecular planarity and rigidity, improves the thermal stability of the material, and enhances the stability of the device. Attached Figure Description

[0012] The accompanying drawings, which are included to provide a further understanding of the invention and form part of this invention, illustrate exemplary embodiments of the invention and are used to explain the invention, but do not constitute an undue limitation of the invention. In the drawings: Figure 1 This is a device structure diagram of Embodiment 1 in the device embodiments of the present invention; Figure 2 This is the electroluminescence spectrum of Example 1 in the device embodiment of the present invention; Figure 3 This is the electroluminescence spectrum of Example 7 in the device embodiment of the present invention. Detailed Implementation

[0013] The technical solution of the present invention will be clearly and completely described below with reference to synthetic embodiments and device embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0014] Synthesis Examples Example 1: Synthesis of Compound 1: ; The first step involved the compound 1-bromo-4-chloro-2-fluorobenzene (0.3 g, 1.5 mmol) and 3,6-di-tert-butyl-9- H - Carbazole (4.2 g, 1.5 mmol) was dissolved in 100 mL of dry... N , N - Dimethylformamide. Then, cesium carbonate (7.3 g, 2.2 mmol) was added under a nitrogen atmosphere. The solution was heated at 150ºC for 20 h, and the reaction mixture was cooled to room temperature. The resulting solution was slowly poured into ice water (500 ml) and stirred with a glass rod. The powder solid was filtered off, dried under vacuum, and further purified by silica gel column chromatography (dichloromethane:hexane (1:10)) to give a white solid 1-1 (yield 77.4%). LC-MS analysis by liquid chromatography-mass spectrometry yielded the following values: theoretical value 468.86, measured value 469.10; ; In the second step, under a nitrogen atmosphere, a hexane solution of n-butyllithium (3.6 mL, 2.5 M, 8.4 mmol) was slowly added dropwise to a solution of compound 1-1 (3.9 g, 8.4 mmol) in anhydrous tetrahydrofuran (50 mL) at -78ºC. After stirring for 2 h, a solution of 9-fluorenone (1.8 g, 10.1 mmol) in anhydrous tetrahydrofuran was slowly added at -60ºC, also under a nitrogen atmosphere. Subsequently, the reaction mixture was slowly heated to room temperature and stirred overnight. The aqueous phase was separated and extracted three times with dichloromethane (100 mL). The organic layers were combined, dried over sodium sulfate, and filtered. After removing the solvent under reduced pressure, the crude product was dissolved in anhydrous dichloromethane (100 mL), and then methanesulfonic acid (5 mL) was slowly added at room temperature. The reaction mixture was stirred for 3 h, then slowly quenched with 100 mL of sodium bicarbonate aqueous solution to separate the aqueous phase, which was extracted with dichloromethane (50 mL). The organic layers were combined, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The product was further purified by silica gel column chromatography (dichloromethane:hexane (1:5)). A yellow solid 1-2 was given (yield 40.1%). LC-MS analysis by liquid chromatography-mass spectrometry yielded a theoretical value of 552.16 and a measured value of 551.24. ; The third step involves adding 1-2 (1.5 g, 2.7 mmol) to dried toluene (20 mL). N 1, N3-Diphenylphenyl-1,3-diamine (0.3 g, 1.2 mmol), Pd2(dba)3 (20.0 mg, 0.02 mmol), tri-tert-butylphosphide tetrafluoroborate (14.0 mg, 0.05 mmol), and sodium tert-butoxide (0.7 g, 7.3 mmol) were mixed and refluxed under nitrogen for 24 h. After cooling to room temperature, the reaction mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate. After filtration and evaporation, the crude product was purified by silica gel column chromatography (dichloromethane:hexane (1:5)) to give a white solid 1-3 (yield 74.3%). LC-MS analysis by liquid chromatography-mass spectrometry yielded the following values: theoretical value 1291.74, measured value 1290.65. ; In the fourth step, under a nitrogen atmosphere, boron tribromide (4.4 g, 17.7 mmol) was added to an ultra-dry o-dichlorobenzene solution containing 2-2 (1.0 g, 0.7 mmol). After sealing the tube, the mixture was heated to 180°C in a sand bath and stirred for 24 h. After cooling to room temperature, the reaction system was quenched with methanol, and the reaction mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate. After filtration and evaporation, the crude product was purified by silica gel column chromatography (dichloromethane:hexane (1:5)) to give a yellow solid compound 1 (yield 39.0%). LC-MS analysis by liquid chromatography-mass spectrometry yielded a theoretical value of 1307.31 and a measured value of 1306.63.

[0015] Example 2: Synthesis of Compound 2: Referring to the synthesis steps and reaction conditions of Example 1, 3,6-di-tert-butyl-9 H -Carbazole was replaced with di(4-tert-butylphenyl)amine to synthesize compound 2. The LC-MS (m / z) values ​​were obtained by liquid chromatography-mass spectrometry: theoretical value 1311.34, measured value 1310.66.

[0016] Example 3: Synthesis of Compound 7: Referring to the synthesis steps and reaction conditions of Example 1, 3,6-di-tert-butyl-9 H -Carbazole was replaced with carbazole to synthesize compound 7. The LC-MS (m / z) values ​​were obtained by liquid chromatography-mass spectrometry: theoretical value was 1082.88, and measured value was 1082.38.

[0017] Example 4: Synthesis of compound 65: Following the synthesis steps and reaction conditions of Example 1, 9-fluorenone was replaced with benzophenone to synthesize compound 65. The LC-MS (m / z) analysis by liquid chromatography-mass spectrometry yielded a theoretical value of 1309.31 and a measured value of 1308.65.

[0018] Example 5: Synthesis of compound 81: Referring to the synthesis steps and reaction conditions of Example 1, the following steps were performed: N 1, N 3-Diphenylphenyl-1,3-diamine replaced with N 1, N 3-Dimethyltrimethylbenzene-1,3-diamine, compound 81, was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the theoretical value was 1393.32, while the measured value was 1392.84.

[0019] Example 6: Synthesis of compound 263: Referring to the synthesis steps and reaction conditions of Example 1, 3,6-di-tert-butyl-9 H - Replace carbazole with carbazole, and replace 9-fluorenone with 3-methylphenylacetone. N 1, N 3-Diphenylphenyl-1,3-diamine replaced with N 1, N 3-Dimethyltrimethylbenzene-1,3-diamine, compound 263, was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the theoretical value was 1087.00, while the measured value was 1086.50.

[0020] Example 7: Synthesis of compound 545: ; In the first step, under a nitrogen atmosphere, a hexane solution of n-butyllithium (3.6 mL, 2.5 M, 8.4 mmol) was slowly added dropwise to a solution of compound 1-1 (3.9 g, 8.4 mmol) in anhydrous tetrahydrofuran (THF) (50 mL) at -78ºC. After stirring for 2 h, 2,7-di-tert-butyl-9-butylene in anhydrous THF was slowly added at -60ºC. HA solution of fluorene-9-one (3.1 g, 10.1 mmol) was prepared under a nitrogen atmosphere. The reaction mixture was then slowly heated to room temperature and stirred overnight. The aqueous phase was separated and extracted three times (100 mL) with dichloromethane. The organic layers were combined, dried over sodium sulfate, and filtered. After removing the solvent under reduced pressure, the crude product was dissolved in anhydrous dichloromethane (100 mL), and then methanesulfonic acid (5 mL) was slowly added at room temperature. The reaction mixture was stirred for 3 h, then slowly quenched with 100 mL of sodium bicarbonate solution. The aqueous phase was separated and extracted with dichloromethane (50 mL). The organic layers were combined, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The product was further purified by silica gel column chromatography (dichloromethane:hexane (1:5)). A yellow solid 2-1 was given (yield 40.2%). LC-MS analysis by liquid chromatography-mass spectrometry yielded a theoretical value of 664.37 and a measured value of 663.36. ; The second step involves adding 2-1 (1.9 g, 2.6 mmol) to dried toluene (20 mL). N 1, N 3-Diphenylphenyl-1,3-diamine (0.3 g, 1.2 mmol), Pd2(dba)3 (20.0 mg, 0.02 mmol), tri-tert-butylphosphide tetrafluoroborate (14.0 mg, 0.05 mmol), and sodium tert-butoxide (0.7 g, 7.3 mmol) were mixed and refluxed under nitrogen for 24 h. After cooling to room temperature, the reaction mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate. After filtration and evaporation, the crude product was purified by silica gel column chromatography (dichloromethane:hexane (1:5)) to give a white solid 2-2 (yield 73.2%). LC-MS analysis by liquid chromatography-mass spectrometry yielded the following values: theoretical value 1516.17, measured value 1515.91. ; In the third step, under a nitrogen atmosphere, boron tribromide (4.4 g, 17.7 mmol) was added to an ultra-dry o-dichlorobenzene solution containing 2-2 (1.0 g, 0.6 mmol). After sealing the tube, the mixture was heated to 180 °C in a sand bath and stirred for 24 h. After cooling to room temperature, the reaction system was quenched with methanol, and the reaction mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate. After filtration and evaporation, the crude product was purified by silica gel column chromatography (dichloromethane:hexane (1:5)) to give a yellow solid compound 545 (yield 38.5%). LC-MS analysis yielded a theoretical value of 1517.72 and a measured value of 1517.86.

[0021] Example 8: Synthesis of compound 549: Referring to the synthesis steps and reaction conditions of Example 7, 3,6-di-tert-butyl-9 H - Carbazole replaced with 3,6-dimethyl-9 H - Carbazole, synthetic compound 549, was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the theoretical value was 1363.42, while the measured value was 1363.69.

[0022] Example 9: Synthesis of compound 552: Referring to the synthesis steps and reaction conditions of Example 7, 3,6-di-tert-butyl-9 H -Carbazole was replaced with diphenylamine to synthesize compound 552. The LC-MS (m / z) analysis by liquid chromatography-mass spectrometry yielded a theoretical value of 1311.34 and a measured value of 1310.66.

[0023] Example 10: Synthesis of compound 553: Referring to the synthesis steps and reaction conditions of Example 7, 2,7-di-tert-butyl-9 H -fluorene-9-one replaced with 9 H ⁻oxanthracene-9-one, compound 553, was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the theoretical value was 1339.31, while the measured value was 1338.36.

[0024] Example 11: Synthesis of compound 561: Referring to the synthesis steps and reaction conditions of Example 7, 2,7-di-tert-butyl-9 H -fluorene-9-one replaced with 9 H -Thioxanthracene-9-one, compound 561, was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the theoretical value was 1357.40, while the measured value was 1356.55.

[0025] Example 12: Synthesis of compound 596: ; In the first step, compounds 1-bromo-4-chloro-2-fluorobenzene (2.1 g, 1.0 mmol) and 3,6-di-tert-butyl-9 H - Carbazole (4.15 g, 1.5 mmol) dissolved in 100 mL of dry... N , N- Dimethylformamide. Then, cesium carbonate (7.25 g, 2.2 mmol) was added under a nitrogen atmosphere. The solution was heated at 160°C for 12 h, and the reaction mixture was cooled to room temperature. The resulting solution was slowly poured into ice water (500 ml) and stirred with a glass rod. The powder solid was filtered off, dried under vacuum, and further purified by silica gel column chromatography (dichloromethane:hexane (1:10)) to give a white solid 3-1 (yield 77.4%). LC-MS analysis by liquid chromatography-mass spectrometry yielded the following values: theoretical value 468.86, measured value 469.10; ; In the second step, under a nitrogen atmosphere, a hexane solution of n-butyllithium (3.6 mL, 2.5 M, 8.4 mmol) was slowly added dropwise to a solution of compound 3-1 (3.9 g, 8.4 mmol) in anhydrous tetrahydrofuran (50 mL) at -78ºC. After stirring for 2 h, a solution of 9H-oxanthracene-9-one (2.0 g, 10.1 mmol) in anhydrous tetrahydrofuran was slowly added at -60ºC, also under a nitrogen atmosphere. Subsequently, the reaction mixture was slowly heated to room temperature and stirred overnight. The aqueous phase was separated and extracted three times with dichloromethane (100 mL). The organic layers were combined, dried over sodium sulfate, and filtered. After removing the solvent under reduced pressure, the crude product was dissolved in anhydrous dichloromethane (100 mL), and then methanesulfonic acid (5 mL) was slowly added at room temperature. The reaction mixture was stirred for 3 hours, then slowly quenched with 100 mL of sodium bicarbonate aqueous solution to separate the aqueous phase, which was extracted with dichloromethane (50 mL). The organic layers were combined, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The product was further purified by silica gel column chromatography (dichloromethane:hexane (1:5)). A yellow solid 3-2 (yield 43.7%) was given. LC-MS analysis by liquid chromatography-mass spectrometry yielded the following values: theoretical value 568.16, measured value 567.23. ; Thirdly, under a nitrogen atmosphere, a hexane solution of n-butyllithium (3.6 mL, 2.5 M, 8.4 mmol) was slowly added dropwise to a solution of compound 3-1 (3.9 g, 8.4 mmol) in anhydrous tetrahydrofuran (THF) (50 mL) at -78ºC. After stirring for 2 h, 9% of the compound in anhydrous tetrahydrofuran was slowly added at -60ºC. HA solution of thioxanthracene-9-one (2.1 g, 10.1 mmol) was prepared under a nitrogen atmosphere. The reaction mixture was then slowly heated to room temperature and stirred overnight. The aqueous phase was separated and extracted three times (100 mL) with dichloromethane. The organic layers were combined, dried over sodium sulfate, and filtered. After removing the solvent under reduced pressure, the crude product was dissolved in anhydrous dichloromethane (100 mL), and then methanesulfonic acid (5 mL) was slowly added at room temperature. The reaction mixture was stirred for 3 h, then slowly quenched with 100 mL of sodium bicarbonate solution. The aqueous phase was separated and extracted with dichloromethane (50 mL). The organic layers were combined, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The product was further purified by silica gel column chromatography (dichloromethane:hexane (1:5)). A yellow solid 3-2 (yield 44.8%) was given. LC-MS analysis by liquid chromatography-mass spectrometry yielded the following values: theoretical value 584.22, test value 583.21. ; The fourth step involves adding 3-2 (0.7 g, 1.2 mmol), 3-3 (0.7 g, 1.2 mmol), and... to dried toluene (20 mL). N 1, N 3-Diphenylphenyl-1,3-diamine (0.3 g, 1.2 mmol), Pd2(dba)3 (20.0 mg, 0.02 mmol), tri-tert-butylphosphide tetrafluoroborate (14.0 mg, 0.05 mmol), and sodium tert-butoxide (0.7 g, 7.3 mmol) were mixed and refluxed under nitrogen for 24 h. After cooling to room temperature, the reaction mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate. After filtration and evaporation, the crude product was purified by silica gel column chromatography (dichloromethane:hexane (1:5)) to give a white solid 3-4 (yield 80.7%). LC-MS analysis by liquid chromatography-mass spectrometry yielded the following values: theoretical value 1339.80, measured value 1339.62. ; In the fifth step, under a nitrogen atmosphere, boron tribromide (4.4 g, 17.7 mmol) was added to an ultra-dry o-dichlorobenzene solution containing 3-4 (2.9 g, 2.2 mmol). After sealing the tube, the mixture was heated to 180°C in a sand bath and stirred for 24 h. After cooling to room temperature, the reaction system was quenched with methanol, and the reaction mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate. After filtration and evaporation, the crude product was purified by silica gel column chromatography (dichloromethane:hexane (1:5)) to give a yellow solid compound 596 (yield 23.5%). LC-MS analysis yielded a theoretical value of 1355.37 and a measured value of 1355.60.

[0026] Example 13: Synthesis of compound 588: Referring to the synthesis steps and reaction conditions of Example 12, 3,6-di-tert-butyl-9 H - Carbazole is replaced with phenothiazine, 9 H -Thioxanth-9-one replaced with 9 H ⁻oxanthracene-9-one, compound 588, was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the theoretical value was 1178.31, while the measured value was 1179.00.

[0027] Example 14: Synthesis of compound 583: Referring to the synthesis steps and reaction conditions of Example 12, 3,6-di-tert-butyl-9 H - Carbazole is replaced with phenoxazine, 9 H -Thioxanth-9-one replaced with 9 H ⁻oxanthracene-9-one, compound 583, was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the theoretical value was 1146.88, while the measured value was 1146.35.

[0028] Example 15: Synthesis of compound 613: ; In the first step, 1-bromo-4-chloro-2-iodobenzene (0.4 g, 1.2 mmol), di(4-tert-butylphenyl)amine (0.33 g, 1.2 mmol), Pd2(dba)3 (20.0 mg, 0.02 mmol), tri-tert-butylphosphotetrafluoroborate (14.0 mg, 0.05 mmol), and sodium tert-butoxide (0.7 g, 7.3 mmol) were mixed in dried toluene (20 mL) and refluxed under nitrogen for 24 h. After cooling to room temperature, the reaction mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate. After filtration and evaporation, the crude product was purified by silica gel column chromatography (dichloromethane:hexane (1:5)) to give a white solid 4-1 (yield 80.7%). LC-MS analysis by liquid chromatography-mass spectrometry yielded the following values: theoretical value 470.88, test value 471.12. ; The second step involves mixing 1-bromo-4-chloro-2-fluorobenzene (0.3 g, 1.2 mmol) and 3,6-di-tert-butyl-9H-carbazole (4.2 g, 1.5 mmol), and dissolving them in 100 mL of dry... N , N- Dimethylformamide. Then, cesium carbonate (7.3 g, 2.2 mmol) was added under a nitrogen atmosphere. The solution was heated at 160°C for 12 h, and the reaction mixture was cooled to room temperature. The resulting solution was slowly poured into ice water (500 ml) and stirred with a glass rod. The powder solid was filtered off, dried under vacuum, and further purified by silica gel column chromatography (dichloromethane:hexane (1:10)) to give a white solid 4-2 (yield 77.4%). LC-MS analysis by liquid chromatography-mass spectrometry yielded the following values: theoretical value 468.86, measured value 469.10; ; In the third step, under a nitrogen atmosphere, a hexane solution of n-butyllithium (3.6 mL, 2.5 M, 8.4 mmol) was slowly added dropwise to a solution of compound 4-1 (3.9 g, 8.4 mmol) in anhydrous tetrahydrofuran (50 mL) at -78ºC. After stirring for 2 h, a solution of 9H-thioxanthracene-9-one (2.1 g, 10.1 mmol) in anhydrous tetrahydrofuran was slowly added at -60ºC, also under a nitrogen atmosphere. Subsequently, the reaction mixture was slowly heated to room temperature and stirred overnight. The aqueous phase was separated and extracted three times with dichloromethane (100 mL). The organic layers were combined, dried over sodium sulfate, and filtered. After removing the solvent under reduced pressure, the crude product was dissolved in anhydrous dichloromethane (100 mL), and then methanesulfonic acid (5 mL) was slowly added at room temperature. The reaction mixture was stirred for 3 hours, then slowly quenched with 100 mL of sodium bicarbonate aqueous solution to separate the aqueous phase, which was extracted with dichloromethane (50 mL). The organic layers were combined, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The product was further purified by silica gel column chromatography (dichloromethane:hexane (1:5)). A yellow solid 4-3 (yield 44.8%) was given. LC-MS analysis by liquid chromatography-mass spectrometry yielded a theoretical value of 586.23 and a measured value of 585.23 (m / z). ; Fourthly, under a nitrogen atmosphere, a hexane solution of n-butyllithium (3.6 mL, 2.5 M, 8.4 mmol) was slowly added dropwise to a solution of compound 4-2 (3.9 g, 8.4 mmol) in anhydrous tetrahydrofuran (50 mL) at -78ºC. After stirring for 2 h, 9-butyllithium in anhydrous tetrahydrofuran was slowly added at -60ºC. HA solution of 2.1 g (10.08 mmol) of oxanthracene-9-one was prepared under a nitrogen atmosphere. The reaction mixture was then slowly heated to room temperature and stirred overnight. The aqueous phase was separated and extracted three times (100 mL) with dichloromethane. The organic layers were combined, dried over sodium sulfate, and filtered. After removing the solvent under reduced pressure, the crude product was dissolved in anhydrous dichloromethane (100 mL), and then methanesulfonic acid (5 mL) was slowly added at room temperature. The reaction mixture was stirred for 3 h, then slowly quenched with 100 mL of sodium bicarbonate solution. The aqueous phase was separated and extracted with dichloromethane (50 mL). The organic layers were combined, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The product was further purified by silica gel column chromatography (dichloromethane:hexane (1:5)). A yellow solid 4-4 (yield 44.1%) was given. LC-MS analysis by liquid chromatography-mass spectrometry yielded the following values: theoretical value 568.16, measured value 567.23. ; In step 5, 4-3 (0.7 g, 1.2 mmol), aniline (0.2 g, 1.2 mmol), Pd2(dba)3 (20.0 mg, 0.02 mmol), tri-tert-butylphosphide tetrafluoroborate (14.0 mg, 0.05 mmol), and sodium tert-butoxide (0.7 g, 7.3 mmol) were mixed in dried toluene (20 mL) and refluxed under nitrogen for 24 h. After cooling to room temperature, the reaction mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate. After filtration and evaporation, the crude product was purified by silica gel column chromatography (dichloromethane:hexane (1:5)) to give a yellow solid 4-5 (yield 80.7%). LC-MS analysis by liquid chromatography-mass spectrometry yielded a theoretical value of 642.90 and a measured value of 642.31. ; In step six, 4-4 (0.7 g, 1.2 mmol), aniline (0.2 g, 1.2 mmol), Pd2(dba)3 (20.0 mg, 0.02 mmol), tri-tert-butylphosphide tetrafluoroborate (14.0 mg, 0.05 mmol), and sodium tert-butoxide (0.7 g, 7.3 mmol) were mixed in dried toluene (20 mL) and refluxed under nitrogen for 24 h. After cooling to room temperature, the reaction mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate. After filtration and evaporation, the crude product was purified by silica gel column chromatography (dichloromethane:hexane (1:5)) to give a yellow solid 4-6 (yield 81.7%). LC-MS analysis by liquid chromatography-mass spectrometry yielded the following values: theoretical value 624.83, test value 624.31. ; In step seven, 4-5 (0.8 g, 1.2 mmol), 4-6 (0.8 g, 1.2 mmol), 1,3-dibromobenzene (0.3 g, 1.2 mmol), Pd2(dba)3 (20.0 mg, 0.02 mmol), tri-tert-butylphosphide tetrafluoroborate (14.0 mg, 0.05 mmol), and sodium tert-butoxide (0.7 g, 7.3 mmol) were mixed in dried toluene (20 mL) and refluxed under nitrogen for 24 h. After cooling to room temperature, the reaction mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate. After filtration and evaporation, the crude product was purified by silica gel column chromatography (dichloromethane:hexane (1:5)) to give a yellow solid 4-7 (yield 80%). LC-MS analysis by liquid chromatography-mass spectrometry yielded a theoretical value of 1341.82 and a measured value of 1341.64. ; In step 8, under a nitrogen atmosphere, boron tribromide (4.4 g, 17.7 mmol) was added to an ultra-dry o-dichlorobenzene solution containing 4-7 (2.9 g, 2.2 mmol). After sealing the tube, the mixture was heated to 180 °C in a sand bath and stirred for 24 h. After cooling to room temperature, the reaction system was quenched with methanol, and the reaction mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate. After filtration and evaporation, the crude product was purified by silica gel column chromatography (dichloromethane:hexane (1:5)) to give a yellow solid compound 613 (yield 22.5%). LC-MS analysis showed a theoretical value of 1357.39 and a measured value of 1357.61.

[0029] Example 16: Synthesis of compound 473: ; The first step involves adding 1-bromo-2,4-difluorobenzene (0.2 g, 1.2 mmol) to 3,6-di-tert-butyl-9-difluorobenzene. H - Carbazole (2.8 g, 1.0 mmol) was mixed and dissolved in 100 mL of dry precipitate. N , N- Dimethylformamide. Then, cesium carbonate (3.9 g, 1.2 mmol) was added under a nitrogen atmosphere. The solution was heated at 100°C for 4 h, and the reaction mixture was cooled to room temperature. The reaction mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate. After filtration and evaporation, it was further purified by silica gel column chromatography (dichloromethane:hexane (1:10)) to give a white solid 5-1 (yield 80.4%). LC-MS analysis by liquid chromatography-mass spectrometry yielded the following values: theoretical value 452.41, measured value 451.13; ; In the second step, under a nitrogen atmosphere, a hexane solution of n-butyllithium (3.6 mL, 2.5 M, 8.4 mmol) was slowly added dropwise to a solution of compound 5-1 (3.8 g, 8.4 mmol) in anhydrous tetrahydrofuran (50 mL) at -78ºC. After stirring for 2 h, a solution of 9-fluorenone (1.8 g, 10.1 mmol) in anhydrous tetrahydrofuran was slowly added at -60ºC, also under a nitrogen atmosphere. Subsequently, the reaction mixture was slowly heated to room temperature and stirred overnight. The aqueous phase was separated and extracted three times with dichloromethane (100 mL). The organic layers were combined, dried over sodium sulfate, and filtered. After removing the solvent under reduced pressure, the crude product was dissolved in anhydrous dichloromethane (100 mL), and then methanesulfonic acid (5 mL) was slowly added at room temperature. The reaction mixture was stirred for 3 hours, then slowly quenched with 100 mL of sodium bicarbonate aqueous solution to separate the aqueous phase, which was extracted with dichloromethane (50 mL). The organic layers were combined, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The product was further purified by silica gel column chromatography (dichloromethane:hexane (1:5)). A yellow solid 5-2 (yield 44.8%) was given. LC-MS analysis by liquid chromatography-mass spectrometry yielded a theoretical value of 535.71 and a measured value of 535.27. ; Thirdly, mix 5-2 (2.1 g, 4 mmol) and 2-methylresorcinol (0.1 g, 1.0 mmol) and dissolve in 20 mL of dry... N , N- Dimethylformamide. Then, cesium carbonate (7.8 g, 2.4 mmol) was added under a nitrogen atmosphere. The solution was heated at 160°C for 10 h, and the reaction mixture was cooled to room temperature. The reaction mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate. After filtration and evaporation, it was further purified by silica gel column chromatography (dichloromethane:hexane (1:10)) to give a white solid 5-3 (yield 78.4%). LC-MS analysis by liquid chromatography-mass spectrometry yielded the following values: theoretical value 1155.54, measured value 1154.58; ; In the fourth step, under a nitrogen atmosphere, boron tribromide (4.4 g, 17.7 mmol) was added to an ultra-dry o-dichlorobenzene solution containing 5-3 (2.5 g, 2.2 mmol). After sealing the tube, the mixture was heated to 180°C in a sand bath and stirred for 24 h. After cooling to room temperature, the reaction system was quenched with methanol, and the reaction mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate. After filtration and evaporation, the crude product was purified by silica gel column chromatography (dichloromethane:hexane (1:5)) to give a yellow-green solid compound 473 (yield 10.5%). LC-MS analysis yielded a theoretical value of 1171.11 and a measured value of 1170.55.

[0030] Example 17: Synthesis of compound 477: Following the synthesis steps and reaction conditions of Example 16, 2-methylresorcinol was replaced with 2-methyl-m-phenylenediol to synthesize compound 477. The LC-MS (m / z) analysis by liquid chromatography-mass spectrometry yielded a theoretical value of 1203.23 and a measured value of 1202.50.

[0031] Example 18: Synthesis of compound 377: ; The first step involves placing 1-2 (1.5 g, 2.7 mmol) of the mixture into dry toluene (20 mL). N,N'-Diphenyl-1,4-phenylenediamine (0.3 g, 1.2 mmol), Pd2(dba)3 (20.0 mg, 0.02 mmol), tri-tert-butylphosphide tetrafluoroborate (14.0 mg, 0.05 mmol), and sodium tert-butoxide (0.7 g, 7.3 mmol) were mixed and refluxed under nitrogen for 24 h. After cooling to room temperature, the reaction mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate. After filtration and evaporation, the crude product was purified by silica gel column chromatography (dichloromethane:hexane (1:5)) to give a white solid 6-1 (yield 77.3%). LC-MS analysis by liquid chromatography-mass spectrometry yielded the following values: theoretical value 1291.74, measured value 1290.65. ; In the second step, under a nitrogen atmosphere, boron tribromide (4.4 g, 17.7 mmol) was added to an ultra-dry o-dichlorobenzene solution containing 6-1 (1.0 g, 0.7 mmol). After sealing the tube, the mixture was heated to 180 °C in a sand bath and stirred for 24 h. After cooling to room temperature, the reaction system was quenched with methanol, and the reaction mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate. After filtration and evaporation, the crude product was purified by silica gel column chromatography (dichloromethane:hexane (1:5)) to give a red solid compound 377 (yield 19.0%). Analysis by liquid chromatography-mass spectrometry (LC-MS) yielded a theoretical value of 1307.31 and a measured value of 1306.63.

[0032] Example 19: Synthesis of compound 393: Referring to the synthesis steps and reaction conditions of Example 18, 9-fluorenone was replaced with benzophenone to synthesize compound 393. The LC-MS (m / z) analysis by liquid chromatography-mass spectrometry yielded a theoretical value of 1309.36 and a measured value of 1308.62.

[0033] Example 20: Synthesis of compound 395: Referring to the synthesis steps and reaction conditions of Example 18, 3,6-di-tert-butyl-9 H -Carbazole was replaced with carbazole, and 9-fluorenone was replaced with benzophenone to synthesize compound 395. The LC-MS (m / z) analysis by liquid chromatography-mass spectrometry yielded a theoretical value of 1086.91 and a measured value of 1086.41.

[0034] The above synthetic examples illustrate representative synthetic routes. Unless otherwise specified, all reagents and instruments used are commercially available conventional products. Some reaction compounds were purchased from a supplier (Zhengzhou Alpha Chemical Co., Ltd.), while some compounds that could not be directly purchased were prepared from commercially available raw materials through simple reactions. All percentages refer to mass percentages. The principles, procedures, routine post-processing, silica gel column chromatography, recrystallization purification, and other techniques of this method are well-known to those skilled in the art and can be fully implemented to obtain the target product.

[0035] In addition, it should be noted that other compounds in this application can be obtained by referring to the preparation methods of the examples listed above, so they will not be listed one by one here.

[0036] Based on the same inventive concept, embodiments of the present invention also provide an organic light-emitting device comprising the compounds of the above embodiments. The following example uses an OLED as an organic light-emitting device for illustration; however, it should be understood that the following detailed description is not a limitation of the present invention, and those skilled in the art can extend the application of the following detailed description to other organic light-emitting devices.

[0037] In one embodiment, the OLED includes a first electrode and a second electrode, and a plurality of organic material layers located between the electrodes. Each organic material layer can be further divided into multiple regions. For example, the organic material layer may include a hole transport region, a light-emitting layer, and an electron transport region.

[0038] In specific embodiments, a substrate can be used below the first electrode or above the second electrode. The substrate is typically made of glass or polymer material with excellent mechanical strength, thermal stability, water resistance, and transparency. Furthermore, thin-film transistors (TFTs) can also be incorporated into the substrate used for displays.

[0039] The first electrode can be formed by sputtering or depositing the material to be used as the first electrode on a substrate. When the first electrode is used as the anode, it can be a transparent conductive oxide material such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), or any combination thereof. When the first electrode is used as the cathode, it can be a metal or alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof.

[0040] Organic material layers can be formed on electrodes using methods such as vacuum thermal evaporation, spin coating, and printing. The compounds used as organic material layers can be small organic molecules, large organic molecules, polymers, and combinations thereof.

[0041] The hole transport region is located between the anode and the light-emitting layer. The hole transport region can be a single-layer hole transport layer (HTL), including a single-layer hole transport layer containing only one compound and a single-layer hole transport layer containing multiple compounds. The hole transport region can also be a multilayer structure including at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL).

[0042] The material for the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenevinyl chloride, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), aromatic amine derivatives as shown in HTL-1 to HTL-20 below; or any combination thereof: .

[0043] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer can be a single compound material or a combination of multiple compounds. For example, the hole injection layer can use one or more compounds from HTL-1 to HTL-20 described above, or one or more compounds from HIL-1 to HIL-3 described below; alternatively, one or more compounds from HTL-1 to HTL-20 can be used to dope one or more compounds from HIL-1 to HIL-3 described below. .

[0044] The luminescent layer comprises one or more compounds as shown in Formula I or Formula II above as luminescent dopant materials, and may also include a host material and / or a sensitizer material. In one aspect of the invention, the host material of the luminescent layer may be selected from, but not limited to, one or more combinations of H-1 to H-8 listed below: .

[0045] In one aspect of the invention, the sensitizer material of the luminescent layer can be a TADF material or a phosphorescent material, and can be selected from, but not limited to, one or more combinations of the following S-1 to S-13: .

[0046] The OLED organic material layer may also include an electron transport region between the light-emitting layer and the cathode. The electron transport region can be a single-layer electron transport layer (ETL), including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds. The electron transport region may also be a multilayer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0047] In a specific example, the electron transport layer material may be selected from, but is not limited to, one or more combinations of ETL-1 to ETL-32 listed below: ; .

[0048] In one example, the device may also include an electron injection layer located between the electron transport layer and the cathode, the electron injection layer material including but not limited to one or more combinations of the following: LiQ, LiF, CsF, Li2O, Cs2CO3, BaO, Na, Li and / or Ca.

[0049] Device Examples To evaluate the luminescence performance of the compounds described in this invention in organic electroluminescent devices, a series of OLED devices based on multilayer organic thin film structures were designed and constructed, and the specific fabrication process is shown below:

[0050] Preparation of Example 1: The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol, baked in a clean environment until all moisture was removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam. The treated ITO transparent conductive layer was placed in a vacuum evaporation chamber. After the system reached a high vacuum, a hole injection layer (HIL) with a thickness of 10 nm was first deposited. This layer used a co-evaporation combination of HTL-1 and HIL-3 (mass ratio 97:3, w / w), with the two materials placed in different evaporation sources. Precise ratio control was achieved by adjusting the evaporation rate. This doping system aims to improve the energy level matching between the anode and the organic layer and reduce the hole injection barrier. A 15 nm thick HTL-1 layer is deposited on top of the hole injection layer as a hole transport layer (HTL). The main function of this layer is to efficiently transport holes and suppress electron back injection, maintaining a good charge balance in the device. Subsequently, a 20 nm thick HTL-2 layer is deposited as an electron blocking layer (EBL) to restrict electron penetration to the hole transport layer, thereby effectively improving the exciton binding ability and recombination efficiency in the light-emitting region. A 30nm thick light-emitting layer (EML) was deposited on the electron blocking layer using a multi-source co-evaporation process. The main material was H-2 and the dopant was compound 1. They were placed in independent evaporation sources and the composite light-emitting film was formed by controlling their evaporation rate ratio to 99:1 (w / w). A 30 nm thick electron transport layer ETL-18 was deposited on the hole blocking layer using a doping system of ETL and LiQ (mass ratio 50:50, w / w). This combination helps to improve the electron transport rate and interface injection efficiency. Depositing 1 nm of LiQ on the electron transport layer as an electron injection layer (EIL) has a very low work function that helps to form an interfacial dipole and improves the injection efficiency of electrons from the Al cathode to the electron transport layer. An Al electrode layer with a thickness of 13 nm is deposited on top of the electron injection layer; this layer serves as the cathode layer. The entire organic layer and cathode evaporation process is completed in a continuous vacuum to avoid interface oxidation or contamination, with the deposition rate set to 0.1 nm / s.

[0051] In the glove box, the vapor-deposited device is coated with UV adhesive using a coating equipment. The coated cover plate is then moved to the lamination section, where the vapor-deposited substrate is placed on top of the cover plate. Finally, the substrate and cover plate are laminated using a bonding equipment and cured with UV adhesive.

[0052] Preparation of Examples 2-30: When forming the light-emitting layer, the corresponding compound in Table 1 was used to replace compound 1 in Example 1, and the organic electroluminescent device was prepared using the same method as in Example 1.

[0053] Preparation of Comparative Examples 1-5: Except that, when forming the light-emitting layer, the corresponding compound in Table 1 was used to replace compound 1 in Example 1, and the organic electroluminescent device was prepared using the same method as in Example 1.

[0054] The structures of Ref-1 to Ref-4 in Table 1 are as follows: .

[0055] Device evaluation: At 10mA / cm 2 The current efficiency of the device examples and comparative examples was determined at a current density of 35 mA / cm². The current efficiency was measured using an IVL (current-voltage-luminance) testing system (Suzhou Fushida Scientific Instruments Co., Ltd.). 2The time required for the brightness to decrease to 95% of the initial brightness at a given current density (LT95) was measured. The lifetime testing system was the OLED lifetime testing system from Suzhou Fosstar Scientific Instruments Co., Ltd.; at 100 cd / m 2 The maximum emission peak position and full width at half maximum (FWHM) were obtained, and the results are shown in Table 1 below: ; As shown in Table 1, compared with the comparative example, the embodiments with the same framework structure exhibit longer emission spectra and narrower full width at half maximum (FWHM). This is because the compounds involved in this invention, by introducing a spirocarbon group to lock the donor on one side, form a planar rigid framework structure with the central benzene ring. This increases the degree of π-conjugation and reduces the degree of excited-state structural relaxation, thereby giving the target molecule a redshifted emission and a narrower spectral emission. Furthermore, the increased molecular rigidity can effectively suppress nonradiative transitions, improve fluorescence quantum efficiency, and enhance molecular thermal stability, thus giving the target molecule higher current efficiency and a longer lifetime.

[0056] Examples 21, 22 and Comparative Examples 5, 6: In Example 1 above, the dopant compounds listed in Table 2 below were used as the light-emitting layer material. The substrate and dopant were vacuum-deposited at a weight ratio of 99:1 to 90:10. Otherwise, the organic light-emitting device was manufactured using the same method as in Example 1. For the organic light-emitting devices manufactured through the above examples and comparative examples, at 10 mA / cm²... 2 The current efficiency was measured at the current density, as shown in Table 2 below: ; It can be confirmed that, compared with their corresponding comparative compounds Ref 2 and Ref 4, compounds 1 and 377 of general formula I satisfy the above general formula, the concentration quenching effect is effectively suppressed due to the three-dimensional spatial steric hindrance effect of the spiral carbon unit, so the current efficiency decreases less with the increase of doping concentration.

[0057] The above embodiments only list the effect data of devices made from a portion of the structures. This is a representative sampling test. Based on the experimental data, the overall data is not significantly different and can represent the effects of other unlisted structures.

[0058] Those skilled in the art will readily recognize that many modifications and variations can be made to this invention without departing from its spirit and scope. Therefore, it is anticipated that this invention covers the modifications and variations provided within the scope of the appended claims and their equivalents. This invention has been illustrated by the above embodiments with respect to the organic electroluminescent materials and organic electroluminescent devices of this invention, but the invention is not limited to the above embodiments, i.e., it does not mean that the invention must rely on the above embodiments to be implemented.

Claims

1. A boron-containing multiple resonance thermally activated delayed fluorescence material, characterized by, The molecular structure is shown in general formula (I) and general formula (II): ； In general formula (I) and general formula (II): Rings A, B, C, and D are independently represented as substituted or unsubstituted C6-C6 groups. 30 Aromatic rings, substituted or unsubstituted C5-C 30 One of the aromatic rings; The ring A and the ring B are not connected, or are connected through a C-C single bond; R1-R 10 Each time it appears, the same or different representations are hydrogen atom, deuterium atom, tritium atom, halogen atom, cyano group, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkenyl, substituted or unsubstituted C1-C 10 Alkynyl, substituted or unsubstituted silyl, substituted or unsubstituted boryl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C6-C 30 Aryloxy group, substituted or unsubstituted aromatic amino group, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C5-C 30 One of the heteroaryl groups; R1-R 10 any two adjacent ones of which are joined together to form a ring or are not joined; X1, X2 each independently represent one of NR 11 , O, S, Se; R 11 Indicated as substituted or unsubstituted C1~C 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted aromatic amino groups, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C5-C 30 One of the heteroaryl groups; Substituents substituting the substitutable groups mentioned above each independently represent substituents substituting the single substitutable group to the maximum allowable number of substituents, optionally selected from deuterium, tritium, halogen, cyano, trifluoromethyl, C1-C3alkyl, C1-C3alkoxy, C1-C3alkylthio, C3-C6cycloalkyl, substituted or unsubstituted arylamino, substituted or unsubstituted C6-C10aryl, and substituted or unsubstituted heteroaryl; and 40 alkyl, C1-C 40 alkoxy, C1-C 40 alkylthio, C3-C 40 cycloalkyl, substituted or unsubstituted arylamino, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C4-C 60 heteroaryl; The heteroatom in the heteroaryl group is optionally selected from one or more of N, O, S, Se, Te or B.

2. The boron-containing multiple-resonance thermally activated delayed fluorescence material according to claim 1, wherein Rings A, B, C, and D are independently represented as substituted or unsubstituted C6-C6 groups. 20 Aromatic rings, substituted or unsubstituted C5-C 20 One of the aromatic rings.

3. The boron-containing multiple-resonance thermally activated delayed fluorescence material according to claim 1, wherein R1-R 10 are each independently selected from the group consisting of hydrogen, deuterium, tritium, a halogen atom, a cyano group, a trifluoromethyl group, or a substituted or unsubstituted group of a silicon group, an amino group, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a s-butyl group, a t-butyl group, a cyclohexyl group, a phenyl group, a methylphenyl group, an i-propylphenyl group, a t-butylphenyl group, a phenol group, a phenylthiol group, a phenylselenol group, an aniline group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a naphthacene group, a fluorenyl group, a 9,9-dimethylfluorenyl group, a 9,9-diphenylfluorenyl group, a spirobifluorenyl group, a dihydophenanthryl group, a dihydropyrenyl group, a tetrahydropyrenyl group, an indenyl group, a furanyl group, a benzofuranyl group, a thienyl group, a benzothienyl group, a pyrrolyl group, an isoindolyl group, a carbazolyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, an acridinyl group, a phenanthridinyl group, a pyrazolyl group, an imidazolyl group, a 1,2-thiazolyl group, a 1,3-thiazolyl group, a pyridazinyl group, a pyrimidinyl group, a quinoxalyl group, a pyrazinyl group, a phenoxazinyl group, a phenothiazinyl group, an azacarbazolyl group, a 1,3,5-triazinyl group, a dimethylboron group, a di(2,4,6-triisopropylphenyl)boron group, or a combination of two or more of the above groups.

4. The boron-containing multiple resonance thermally activated delayed fluorescence material according to any one of claims 1 to 3, characterized in that, The boron-containing multiple resonance delayed fluorescence material is any one of the following compounds: ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； 。 5. An organic electroluminescent device having an anode, a cathode, an organic layer, the organic layer comprising an emission layer, characterized in that The light-emitting side comprises the boron-containing multiple resonance type thermally activated delayed fluorescence material according to any one of claims 1 to 4.

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