An organic electroluminescent material based on a triazine ring structure and an organic electroluminescent device
By designing organic electroluminescent materials based on triazine ring structures and using specific group combinations to form AD or ADA structures, the problem of insufficient performance of existing materials has been solved, and the high efficiency of light emission and long lifetime of the device have been achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- NANJING TOPTO MATERIALS CO LTD
- Filing Date
- 2019-11-28
- Publication Date
- 2026-05-12
AI Technical Summary
The performance of existing organic electroluminescent materials has not yet met the high requirements of panel manufacturers, and there is a need to improve the luminous efficiency and lifespan of devices.
Design an organic electroluminescent material based on a triazine ring structure, and form an AD or ADA structure through specific group combinations to improve the HOMO and T1 energy levels, thereby enhancing hole blocking ability and triplet exciton confinement ability.
This improved the exciton utilization rate of the material, thereby enhancing the luminous efficiency and lifespan of the device.
Smart Images
Figure CN115772162B_ABST
Abstract
Description
[0001] This application is a divisional application of application number 2019111862917, filed on November 28, 2019, entitled "An organic electroluminescent material and organic electroluminescent device based on a triazine ring structure". Technical Field
[0002] This invention relates to the field of organic electroluminescent materials, and more specifically to an organic electroluminescent material and an organic electroluminescent device based on a triazine ring structure. Background Technology
[0003] Organic light-emitting devices (OLEDs) are self-emissive light-emitting devices that utilize the following principle: when an electric field is applied, fluorescent material emits light through the recombination of holes injected at the positive electrode and electrons injected at the negative electrode. These self-emissive devices possess characteristics such as low voltage, high brightness, wide viewing angle, fast response, and good temperature adaptability. Furthermore, they are ultra-thin and can be fabricated on flexible panels, making them widely used in mobile phones, tablets, televisions, lighting, and other fields.
[0004] Organic electroluminescent devices (OLEDs) have a sandwich-like structure, consisting of electrode material layers and organic functional materials sandwiched between different electrode layers or on their own. These various functional materials are stacked together according to their intended use to form the OLED. As a current-carrying device, when a voltage is applied to the two electrodes of the OLED, positive and negative charges are generated in the organic functional material layers through the action of an electric field. These charges then recombine in the light-emitting layer, producing light; this process is called electroluminescence.
[0005] Research on improving the performance of organic electroluminescent devices includes reducing the driving voltage, increasing luminous efficiency, and extending lifespan. To continuously improve the performance of organic electroluminescent devices, innovation in their structure and fabrication processes is needed, along with ongoing research and innovation in organic electroluminescent functional materials to create higher-performance organic electroluminescent functional materials.
[0006] In terms of the actual needs of the current organic electroluminescent industry, the development of organic electroluminescent materials is still far from sufficient and lags behind the requirements of panel manufacturers. Summary of the Invention
[0007] Purpose of the invention: To address the above-mentioned technical problems, the present invention provides an organic electroluminescent material and an organic electroluminescent device based on a triazine ring structure.
[0008] To achieve the above-mentioned objectives, the technical solution adopted by this invention is as follows:
[0009] An organic electroluminescent material based on a triazine ring structure has the following structural formula (1):
[0010]
[0011] Among them, R1 and R2 are independently substituted or unsubstituted C3-C6 cycloalkyl groups, substituted or unsubstituted C6-C30 aromatic groups, or substituted or unsubstituted C5-C30 heteroaromatic groups.
[0012] L1 and L2 are each independently phenylene;
[0013] R3 is any one of a substituted or unsubstituted C6-C30 aromatic group or a substituted or unsubstituted C5-C30 heteroaromatic group;
[0014] R4 is any one of hydrogen, deuterium, or cyano;
[0015] m and n are each independently 0 or 1.
[0016] Furthermore, R1 and R2 are each independently cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, fluorenyl, oxofluorenyl, 9,9-dimethylfluorenyl, 9,9'-spirodifluorenyl, 9,9-diphenylfluorenyl, thiofluorenyl, carbazole, benzocarbazole, and N-phenylcarbazole.
[0017] The cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, fluorenyl, oxofluorenyl, 9,9-dimethylfluorenyl, 9,9'-spirodifluorenyl, 9,9-diphenylfluorenyl, thiofluorenyl, carbazole, benzocarbazole, and N-phenylcarbazole are unsubstituted or obtained by substituting at least one hydrogen atom with deuterium, C1-C4 alkyl, or benzene.
[0018] Preferably, R1 and R2 are each independently cyclohexane, phenyl, biphenyl, naphthyl, phenanthrene, oxofluorenyl, 9,9'-spirodifluorene, carbazolyl, N-phenylcarbazolyl, deuterated phenyl, tert-butylated phenyl, isopropylated phenyl, or phenyl-substituted oxofluorenyl.
[0019] Preferably, R1 and R2 contain an oxofluorene group.
[0020] Further, R3 is any one of substituted or unsubstituted naphthyl, substituted or unsubstituted anthraceneyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted benzophenanthryl, or substituted or unsubstituted pyrene.
[0021] Preferably, R3 is any one of unsubstituted naphthyl, anthraceneyl, phenanthryl, and pyreneyl.
[0022] Furthermore, the organic electroluminescent material contains at least one of the following compounds:
[0023]
[0024]
[0025]
[0026]
[0027]
[0028]
[0029]
[0030]
[0031]
[0032]
[0033]
[0034]
[0035]
[0036]
[0037] The above-mentioned organic electroluminescent materials are used in the fabrication of organic electroluminescent devices.
[0038] An organic electroluminescent device includes: an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode stacked sequentially; the electron transport layer contains the aforementioned organic electroluminescent material.
[0039] This invention discloses an organic electroluminescent display device containing the above-mentioned organic electroluminescent device.
[0040] The present invention further discloses an organic electroluminescent lighting device containing the above-mentioned organic electroluminescent device.
[0041] The room temperature described in this invention is 25±5℃.
[0042] The beneficial effects of this invention are:
[0043] The organic electroluminescent material designed in this invention features an electron-withdrawing triazine group. This triazine group is linked with R1, R2, R3, R4, L1, and L2 groups to form an AD or ADA structure. This structure gives the material high HOMO (highest occupied molecular orbital) and high T1 (triplet state) energy levels. The high HOMO level enhances the material's hole-blocking ability, trapping holes in the emitting layer where they meet electrons to form excitons, thus improving exciton utilization. Simultaneously, the high T1 level provides excellent triplet exciton blocking capability, confining triplet excitons within the emitting layer. Using this material as an electron transport material can further improve the luminous efficiency and lifespan of devices fabricated using it. Attached Figure Description
[0044] Figure 1 This is a schematic diagram of the structure of the organic electroluminescent device provided by the present invention;
[0045] The numbers in the diagram represent:
[0046] 1-Cathode, 2-Electron injection layer, 3-Electron transport layer, 4-Light emission layer, 5-Hole transport layer, 6-Hole injection layer, 7-Anode.
[0047] Figure 2 This is a graph showing the HOMO value of the organic electroluminescent material 1 of the present invention. Figure 2 It can be seen that the HOMO value of the organic electroluminescent material 1 of the present invention is 6.41.
[0048] Figure 3 This is the TGA spectrum of the organic electroluminescent material 13 of the present invention, from... Figure 3 It is known that the Td value of the organic light-emitting material 13 of the present invention is 390.50℃. Detailed Implementation
[0049] Unless otherwise specified in the examples, the procedures should be performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products.
[0050] Example 1:
[0051]
[0052] The synthesis method of organic electroluminescent material (1) is as follows:
[0053] S1:
[0054]
[0055] Compound 1-a (5.05 g, 317.76 g / mol, 15.89 mmol), compound 1-b (1.1 eq, 2.13 g, 121.93 g / mol, 17.47 mmol), and sodium carbonate (2 eq, 3.37 g, 105.99 g / mol, 31.77 mmol) were added to ethylene glycol diamine ether (100 g, 20 times the mass of compound 1-a) and water (100 g, 20 times the mass of compound 1-a), and the mixture was stirred. After homogenization, tris(o-tolyl)phosphine (5% eq, 0.24 g, 304.37 g / mol, 0.79 mmol) and palladium(II) acetate (1% eq, 0.04 g, 224.51 g / mol, 0.16 mmol) were added sequentially. The mixture was heated to reflux and reacted for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 1-c (4.33 g, yield 87.3%), MS (EI): 314 (M+).
[0056] S2:
[0057]
[0058] Compound 1-c (4 g, 314.96 g / mol, 12.78 mmol), compound 1-d (1.1 eq, 2.98 g, 212.01 g / mol, 14.06 mmol), and sodium carbonate (2 eq, 2.71 g, 105.99 g / mol, 25.57 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 1-c) and water (80 g, 20 times the mass of compound 1-c), and the mixture was stirred until homogeneous. Tris(o-tolyl)phosphine (5% eq, 0.19 g, 304.37 g / mol, 0.64 mmol) and palladium(II) acetate (1% eq, 0.03 g, 224.51 g / mol, 0.13 mmol) were added sequentially. The mixture was heated to reflux and reacted for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 1-e (4.19 g, yield 81.6%), MS (EI): 402 (M+).
[0059] S3:
[0060]
[0061] Compound 1-e (4 g, 402.24 g / mol, 9.97 mmol), compound 1-f (1.1 eq, 3.83 g, 349.19 g / mol, 10.97 mmol), and sodium carbonate (2 eq, 2.11 g, 105.99 g / mol, 19.95 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 1-e) and water (80 g, 20 times the mass of compound 1-e), stirred and mixed thoroughly, and then added sequentially... Tris(o-tolyl)phosphine (5% eq, 0.15 g, 304.37 g / mol, 0.5 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.1 mmol) were added, and the mixture was heated to reflux for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain a crude product. The crude product was then subjected to column chromatography to obtain an organic electroluminescent material (1) (4.64 g, yield 74.2%), MS (EI): 626 (M+).
[0062] Example 2:
[0063]
[0064] The synthesis method of organic electroluminescent material (2) is as follows:
[0065]
[0066] Compound 2-a (4 g, 402.24 g / mol, 9.97 mmol), compound 2-b (1.1 eq, 3.83 g, 349.19 g / mol, 10.97 mmol), and sodium carbonate (2 eq, 2.11 g, 105.99 g / mol, 19.95 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 2-a) and water (80 g, 20 times the mass of compound 2-a), stirred and mixed thoroughly, and then added sequentially... Tris(o-tolyl)phosphine (5% eq, 0.15 g, 304.37 g / mol, 0.5 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.1 mmol) were added, and the mixture was heated to reflux for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain a crude product. The crude product was then subjected to column chromatography to obtain organic electroluminescent material (2) (4.49 g, yield 71.9%), MS (EI): 626 (M+).
[0067] Example 3:
[0068]
[0069] The synthesis method of organic electroluminescent material (5) is as follows:
[0070] S1:
[0071]
[0072] Compound 3-a (4 g, 314.96 g / mol, 12.778 mmol), compound 3-b (1.1 eq, 2.98 g, 212.01 g / mol, 14.06 mmol), and sodium carbonate (2 eq, 2.71 g, 105.99 g / mol, 25.57 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 3-a) and water (80 g, 20 times the mass of compound 3-a), and the mixture was stirred until homogeneous. Tris(o-tolyl)phosphine (5% eq, 0.19 g, 304.37 g / mol, 0.64 mmol) and palladium(II) acetate (1% eq, 0.03 g, 224.51 g / mol, 0.13 mmol) were added sequentially. The mixture was heated to reflux and reacted for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 3-c (4.29 g, yield 83.4%), MS (EI): 402 (M+).
[0073] S2:
[0074]
[0075] Compound 3-c (4 g, 402.24 g / mol, 9.97 mmol), compound 3-d (1.1 eq, 3.83 g, 349.19 g / mol, 10.97 mmol), and sodium carbonate (2 eq, 2.11 g, 105.99 g / mol, 19.95 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 3-c) and water (80 g, 20 times the mass of compound 3-c), stirred and mixed thoroughly, and then... Tris(o-tolyl)phosphine (5% eq, 0.15 g, 304.37 g / mol, 0.5 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.1 mmol) were added one by one. After the mixture was heated to reflux and reacted for 15 h, the organic phase was separated, washed with water and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain the organic electroluminescent material (5) (4.7 g, yield 75.3%), MS (EI): 626 (M+).
[0076] Example 4:
[0077]
[0078] The synthesis method of organic electroluminescent material (11) is as follows:
[0079] S1:
[0080]
[0081] Compound 4-a (4 g, 314.96 g / mol, 12.78 mmol), compound 4-b (1.1 eq, 2.98 g, 212.01 g / mol, 14.06 mmol), and sodium carbonate (2 eq, 2.71 g, 105.99 g / mol, 25.57 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 4-a) and water (80 g, 20 times the mass of compound 4-a), and the mixture was stirred until homogeneous. Tris(o-tolyl)phosphine (5% eq, 0.19 g, 304.37 g / mol, 0.64 mmol) and palladium(II) acetate (1% eq, 0.03 g, 224.51 g / mol, 0.13 mmol) were added sequentially. The mixture was heated to reflux and reacted for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 4-c (4.27 g, yield 83.0%), MS (EI): 402 (M+).
[0082] S2:
[0083]
[0084] Compound 4-c (4 g, 402.24 g / mol, 9.97 mmol), compound 4-d (1.1 eq, 3.83 g, 349.19 g / mol, 10.97 mmol), and sodium carbonate (2 eq, 2.11 g, 105.99 g / mol, 19.95 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 4-c) and water (80 g, 20 times the mass of compound 4-c), stirred and mixed thoroughly, and then added sequentially... Tris(o-tolyl)phosphine (5% eq, 0.15 g, 304.37 g / mol, 0.5 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.1 mmol) were added, and the mixture was heated to reflux for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain a crude product. The crude product was then subjected to column chromatography to obtain an organic electroluminescent material (11) (4.51 g, yield 72.2%), MS (EI): 626 (M+).
[0085] Example 5:
[0086]
[0087] The synthesis method of organic electroluminescent material (13) is as follows:
[0088] S1:
[0089]
[0090] Compound 5-a (4 g, 314.96 g / mol, 12.78 mmol), compound 5-b (1.1 eq, 2.98 g, 212.01 g / mol, 14.06 mmol), and sodium carbonate (2 eq, 2.71 g, 105.99 g / mol, 25.57 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 5-a) and water (80 g, 20 times the mass of compound 5-a), and the mixture was stirred until homogeneous. Tris(o-tolyl)phosphine (5% eq, 0.19 g, 304.37 g / mol, 0.64 mmol) and palladium(II) acetate (1% eq, 0.03 g, 224.51 g / mol, 0.13 mmol) were added sequentially. The mixture was heated to reflux for 15 h, and the organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 5-c (4.01 g, yield 78.3%), MS (EI): 402 (M+).
[0091] S2:
[0092]
[0093] Compound 5-c (4 g, 402.24 g / mol, 9.97 mmol), compound 5-d (1.1 eq, 3.83 g, 349.13 g / mol, 10.97 mmol), and sodium carbonate (2 eq, 2.11 g, 105.99 g / mol, 19.95 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 5-c) and water (80 g, 20 times the mass of compound 5-c), stirred and mixed thoroughly, and then added sequentially... Tris(o-tolyl)phosphine (5% eq, 0.15 g, 304.37 g / mol, 0.5 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.1 mmol) were added, and the mixture was heated to reflux for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain a crude product. The crude product was then subjected to column chromatography to obtain an organic electroluminescent material (13) (4.77 g, yield 76.5%), MS (EI): 626 (M+).
[0094] Example 6:
[0095]
[0096] The synthesis method of organic electroluminescent material (17) is as follows:
[0097] S1:
[0098]
[0099] Compound 6-a (5 g, 314.96 g / mol, 15.89 mmol), compound 6-b (1.1 eq, 3.46 g, 198.03 g / mol, 17.47 mmol), and sodium carbonate (2 eq, 3.37 g, 105.99 g / mol, 31.77 mmol) were added to ethylene glycol diamine ether (100 g, 20 times the mass of compound 6-a) and water (100 g, 20 times the mass of compound 6-a), and the mixture was stirred until homogeneous. Tris(o-tolyl)phosphine (5% eq, 0.24 g, 304.37 g / mol, 0.79 mmol) and palladium(II) acetate (1% eq, 0.04 g, 224.51 g / mol, 0.16 mmol) were added sequentially. The mixture was heated to reflux and reacted for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 6-c (5.16 g, yield 83.7%), MS (EI): 388 (M+).
[0100] S2:
[0101]
[0102] Compound 6-c (5 g, 391.06 g / mol, 12.86 mmol), compound 6-d (1.1 eq, 3 g, 212.01 g / mol, 14.14 mmol), and sodium carbonate (2 eq, 2.73 g, 105.99 g / mol, 25.71 mmol) were added to ethylene glycol diamine ether (100 g, 20 times the mass of compound 6-c) and water (100 g, 20 times the mass of compound 6-c), and the mixture was stirred until homogeneous. Tris(o-tolyl)phosphine (5% eq, 0.2 g, 304.37 g / mol, 0.64 mmol) and palladium(II) acetate (1% eq, 0.03 g, 224.51 g / mol, 0.13 mmol) were added sequentially. The mixture was heated to reflux for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 6-e (4.75 g, yield 77.2%), MS (EI): 478 (M+).
[0103] S3:
[0104]
[0105] Compound 6-e (4.5 g, 478.34 g / mol, 9.43 mmol), compound 6-f (1.1 eq, 3.62 g, 349.13 g / mol, 10.38 mmol) and sodium carbonate (2 eq, 2 g, 105.99 g / mol, 18.87 mmol) were added into ethyleneglycol dimethyl ether (90 g, 20 times mass of compound 6-e) and water (90 g, 20 times mass of compound 6-e), after stirring and mixing, tris(o-tolyl)phosphine (5% eq, 0.14 g, 304.37 g / mol, 0.47 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.09 mmol) were added in turn, after reaction at reflux for 15 h, the organic phase was separated, washed with water and concentrated under reduced pressure to obtain a crude product, which was subjected to column chromatography to obtain organic electroluminescent material (17) (4.74 g, yield 71.6%), MS (EI): 702 (M+).
[0106] Example 7:
[0107]
[0108] The synthetic method of organic electroluminescent material (36) is as follows:
[0109] S1:
[0110]
[0111] Compound 7-a (5 g, 317.76 g / mol, 15.89 mmol), compound 7-b (1.1 eq, 3.01 g, 171.99 g / mol, 17.47 mmol) and sodium carbonate (2 eq, 3.37 g, 105.99 g / mol, 31.77 mmol) were added into ethyleneglycol dimethyl ether (100 g, 20 times mass of compound 7-a) and water (100 g, 20 times mass of compound 7-a), after stirring and mixing, tris(o-tolyl)phosphine (5% eq, 0.24 g, 304.37 g / mol, 0.79 mmol) and palladium(II) acetate (1% eq, 0.04 g, 224.51 g / mol, 0.16 mmol) were added in turn, after reaction at reflux for 15 h, the organic phase was separated, washed with water and concentrated under reduced pressure to obtain a crude product, which was subjected to column chromatography to obtain compound 7-c (4.2 g, yield 72.4%), MS (EI): 365 (M+).
[0112] S2:
[0113]
[0114] Compound 7-c (4 g, 365.02 g / mol, 11.02 mmol), compound 7-d (1.1 eq, 2.57 g, 212.01 g / mol, 12.12 mmol), and sodium carbonate (2 eq, 2.34 g, 105.99 g / mol, 22.04 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 7-c) and water (80 g, 20 times the mass of compound 7-c), and the mixture was stirred until homogeneous. Tris(o-tolyl)phosphine (5% eq, 0.17 g, 304.37 g / mol, 0.55 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.11 mmol) were added sequentially. The mixture was heated to reflux for 15 h, and the organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 7-e (3.74 g, yield 75.2%), MS (EI): 452 (M+).
[0115] S3:
[0116]
[0117] Compound 7-e (3.5 g, 452.30 g / mol, 7.76 mmol), compound 7-f (1.1 eq, 2.98 g, 349.19 g / mol, 8.54 mmol), and sodium carbonate (2 eq, 1.64 g, 105.99 g / mol, 15.52 mmol) were added to ethylene glycol diamine ether (70 g, 20 times the mass of compound 7-e) and water (70 g, 20 times the mass of compound 7-e). The mixture was stirred until homogeneous, and then added sequentially... Tris(o-tolyl)phosphine (5% eq, 0.12 g, 304.37 g / mol, 0.39 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.08 mmol) were added, and the mixture was heated to reflux for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain a crude product. The crude product was then subjected to column chromatography to obtain an organic electroluminescent material (36) (3.54 g, yield 67.4%), MS (EI): 676 (M+).
[0118] Example 8:
[0119]
[0120] The synthesis method of organic electroluminescent material (53) is as follows:
[0121] S1:
[0122]
[0123] Compound 8-a (5 g, 317.76 g / mol, 15.89 mmol), compound 8-b (1.1 eq, 3.88 g, 222.05 g / mol, 17.47 mmol), and sodium carbonate (2 eq, 3.37 g, 105.99 g / mol, 31.77 mmol) were added to ethylene glycol diamine ether (100 g, 20 times the mass of compound 8-a) and water (100 g, 20 times the mass of compound 8-a), and the mixture was stirred until homogeneous. Then, tris(o-tolyl)phosphine (5% eq, 0.24 g, 304.37 g / mol, 0.79 mmol) and palladium(II) acetate (1% eq, 0.04 g, 224.51 g / mol, 0.16 mmol) were added sequentially. The mixture was heated to reflux and reacted for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 8-c (4.6 g, yield 70.2%), MS (EI): 415 (M+).
[0124] S2:
[0125]
[0126] Compound 8-c (4 g, 415.08 g / mol, 9.69 mmol), compound 8-d (1.1 eq, 2.26 g, 212.01 g / mol, 10.66 mmol), and sodium carbonate (2 eq, 2.05 g, 105.99 g / mol, 19.37 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 8-c) and water (80 g, 20 times the mass of compound 8-c), and the mixture was stirred until homogeneous. Tris(o-tolyl)phosphine (5% eq, 0.15 g, 304.37 g / mol, 0.48 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.1 mmol) were added sequentially. The mixture was heated to reflux and reacted for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 8-e (3.57 g, yield 73.6%), MS (EI): 502 (M+).
[0127] S3:
[0128]
[0129] Compound 8-e (3 g, 502.36 g / mol, 5.99 mmol), compound 8-f (1.1 eq, 2.3 g, 349.19 g / mol, 6.59 mmol), and sodium carbonate (2 eq, 1.27 g, 105.99 g / mol, 11.97 mmol) were added to ethylene glycol diamine ether (60 g, 20 times the mass of compound 8-e) and water (60 g, 20 times the mass of compound 8-e). The mixture was stirred until homogeneous, and then added sequentially... Tris(o-tolyl)phosphine (5% eq, 0.09 g, 304.37 g / mol, 0.3 mmol) and palladium(II) acetate (1% eq, 0.01 g, 224.51 g / mol, 0.06 mmol) were heated to reflux for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain a crude product. The crude product was then subjected to column chromatography to obtain an organic electroluminescent material (53) (2.86 g, yield 65.8%), MS (EI): 726 (M+).
[0130] Example 9:
[0131]
[0132] The synthesis method of organic electroluminescent material (73) is as follows:
[0133] S1:
[0134]
[0135] Compound 9-a (5 g, 317.76 g / mol, 15.89 mmol), compound 9-b (1.1 eq, 3.71 g, 212.01 g / mol, 17.47 mmol), and sodium carbonate (2 eq, 3.37 g, 105.99 g / mol, 31.77 mmol) were added to ethylene glycol diamine ether (100 g, 20 times the mass of compound 9-a) and water (100 g, 20 times the mass of compound 9-a), and the mixture was stirred until homogeneous. Tris(o-tolyl)phosphine (5% eq, 0.24 g, 304.37 g / mol, 0.79 mmol) and palladium(II) acetate (1% eq, 0.04 g, 224.51 g / mol, 0.16 mmol) were added sequentially. The mixture was heated to reflux and reacted for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 9-c (4.92 g, yield 76.4%), MS (EI): 405 (M+).
[0136] S2:
[0137]
[0138] Compound 9-c (4 g, 405.04 g / mol, 9.93 mmol), compound 9-d (1.1 eq, 3.93 g, 360.21 g / mol, 10.92 mmol), and sodium carbonate (2 eq, 2.1 g, 105.99 g / mol, 19.86 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 9-c) and water (80 g, 20 times the mass of compound 9-c), and the mixture was stirred until homogeneous. Tris(o-tolyl)phosphine (5% eq, 0.15 g, 304.37 g / mol, 0.5 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.1 mmol) were added sequentially. The mixture was heated to reflux and reacted for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 9-e (3.45 g, yield 54.2%), MS (EI): 640 (M+).
[0139] S3:
[0140]
[0141] Compound 9-e (3 g, 640.53 g / mol, 4.69 mmol), compound 9-f (1.1 eq, 1.8 g, 349.19 g / mol, 5.16 mmol), and sodium carbonate (2 eq, 1 g, 105.99 g / mol, 9.39 mmol) were added to ethylene glycol diamine ether (60 g, 20 times the mass of compound 9-e) and water (60 g, 20 times the mass of compound 9-e). The mixture was stirred until homogeneous, and then tri( o-Tolylphosphine (5% eq, 0.07 g, 304.37 g / mol, 0.23 mmol) and palladium(II) acetate (1% eq, 0.01 g, 224.51 g / mol, 0.05 mmol) were heated to reflux for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain a crude product. The crude product was then subjected to column chromatography to obtain an organic electroluminescent material (73) (2.46 g, yield 60.8%), MS (EI): 864 (M+).
[0142] Example 10:
[0143]
[0144] The synthesis method of organic electroluminescent material (73) is as follows:
[0145] S1:
[0146]
[0147] Compound 10-a (5 g, 317.76 g / mol, 15.89 mmol), compound 10-b (1.1 eq, 3.71 g, 212.01 g / mol, 17.47 mmol), and sodium carbonate (2 eq, 3.37 g, 105.99 g / mol, 31.77 mmol) were added to ethylene glycol diamine ether (100 g, 20 times the mass of compound 10-a) and water (100 g, 20 times the mass of compound 10-a), and the mixture was stirred. After homogenization, tris(o-tolyl)phosphine (5% eq, 0.24 g, 304.37 g / mol, 0.79 mmol) and palladium(II) acetate (1% eq, 0.04 g, 224.51 g / mol, 0.16 mmol) were added sequentially. The mixture was heated to reflux and reacted for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 10-c (4.7 g, yield 73.5%), MS (EI): 405 (M+).
[0148] S2:
[0149]
[0150] Compound 10-c (4 g, 405.04 g / mol, 9.93 mmol), compound 10-d (1.1 eq, 2.32 g, 212.01 g / mol, 10.92 mmol), and sodium carbonate (2 eq, 2.1 g, 105.99 g / mol, 19.86 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 10-c) and water (80 g, 20 times the mass of compound 10-c), and the mixture was stirred until homogeneous. Then, tris(o-tolyl)phosphine (5% eq, 0.15 g, 304.37 g / mol, 0.5 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.1 mmol) were added sequentially. After the mixture was heated to reflux for 15 h, the organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 10-e (3.48 g, yield 71.4%), MS (EI): 492 (M+).
[0151] S3:
[0152]
[0153] Compound 10-e (3 g, 492.32 g / mol, 8.15 mmol), compound 10-f (1.1 eq, 3.13 g, 349.19 g / mol, 8.96 mmol), and sodium carbonate (2 eq, 1.73 g, 105.99 g / mol, 16.29 mmol) were added to ethylene glycol diamine ether (60 g, 20 times the mass of compound 10-e) and water (60 g, 20 times the mass of compound 10-e), and the mixture was stirred until homogeneous. Tris(o-tolyl)phosphine (5% eq, 0.12 g, 304.37 g / mol, 0.41 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.08 mmol) were added sequentially. After reflux for 15 h, the organic phase was separated, washed with water, and concentrated under reduced pressure to obtain a crude product. The crude product was then subjected to column chromatography to obtain an organic electroluminescent material (97) (4 g, yield 68.6%), MS (EI): 716 (M+).
[0154] Example 11:
[0155]
[0156] The synthesis method of the organic electroluminescent material (121) is as follows:
[0157]
[0158] Compound 11-a (4 g, 402.24 g / mol, 9.97 mmol), compound 111-b (1.1 eq, 4.38 g, 399.25 g / mol, 10.97 mmol), and sodium carbonate (2 eq, 2.11 g, 105.99 g / mol, 19.95 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 11-a) and water (80 g, 20 times the mass of compound 11-a), and the mixture was stirred until homogeneous. Tris(o-tolyl)phosphine (5% eq, 0.15 g, 304.37 g / mol, 0.5 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.1 mmol) were added sequentially. After reflux for 15 h, the organic phase was separated, washed with water, and concentrated under reduced pressure to obtain a crude product. The crude product was then subjected to column chromatography to obtain the organic electroluminescent material (121) (4.8 g, yield 71.2%), MS (EI): 676 (M+).
[0159] Example 12:
[0160]
[0161] The synthesis method of the organic electroluminescent material (126) is as follows:
[0162]
[0163] Compound 12-a (4 g, 402.24 g / mol, 9.97 mmol), compound 12-b (1.1 eq, 4.38 g, 399.25 g / mol, 10.97 mmol), and sodium carbonate (2 eq, 2.11 g, 105.99 g / mol, 19.95 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 12-a) and water (80 g, 20 times the mass of compound 12-a), stirred and mixed thoroughly, and then... Tris(o-tolyl)phosphine (5% eq, 0.15 g, 304.37 g / mol, 0.5 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.1 mmol) were added one-time, and the mixture was heated to reflux for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain a crude product. The crude product was then subjected to column chromatography to obtain the organic electroluminescent material (126) (4.54 g, yield 67.3%), MS (EI): 676 (M+).
[0164] Example 13:
[0165]
[0166] The synthesis method of organic electroluminescent material (151) is as follows:
[0167] S1:
[0168]
[0169] Compound 13-a (5 g, 317.76 g / mol, 15.89 mmol), compound 13-b (1.1 eq, 3.46 g, 198.03 g / mol, 17.47 mmol), and sodium carbonate (2 eq, 3.37 g, 105.99 g / mol, 31.77 mmol) were added to ethylene glycol diamine ether (100 g, 20 times the mass of compound 13-a) and water (100 g, 20 times the mass of compound 13-a), and the mixture was stirred. After homogenization, tris(o-tolyl)phosphine (5% eq, 0.24 g, 304.37 g / mol, 0.79 mmol) and palladium(II) acetate (1% eq, 0.04 g, 224.51 g / mol, 0.16 mmol) were added sequentially. The mixture was heated to reflux and reacted for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 13-c (5.01 g, yield 80.6%), MS (EI): 391 (M+).
[0170] S2:
[0171]
[0172] Compound 13-c (4.5 g, 391.06 g / mol, 11.57 mmol), compound 13-d (1.1 eq, 2.7 g, 212.01 g / mol, 12.73 mmol), and sodium carbonate (2 eq, 2.45 g, 105.99 g / mol, 23.14 mmol) were added to ethylene glycol diamine ether (90 g, 20 times the mass of compound 13-c) and water (90 g, 20 times the mass of compound 13-c), and the mixture was stirred until homogeneous. Then, tris(o-tolyl)phosphine (5% eq, 0.18 g, 304.37 g / mol, 0.58 mmol) and palladium(II) acetate (1% eq, 0.03 g, 224.51 g / mol, 0.12 mmol) were added sequentially. After the mixture was heated to reflux for 15 h, the organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 13-e (4.07 g, yield 73.8%), MS (EI): 478 (M+).
[0173] S3:
[0174]
[0175] Compound 13-e (4 g, 478.34 g / mol, 8.38 mmol), compound 13-f (1.1 eq, 3.68 g, 399.25 g / mol, 9.22 mmol), and sodium carbonate (2 eq, 1.78 g, 105.99 g / mol, 16.77 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 13-e) and water (80 g, 20 times the mass of compound 13-e), stirred and mixed thoroughly, and then... Tris(o-tolyl)phosphine (5% eq, 0.13 g, 304.37 g / mol, 0.42 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.08 mmol) were added one-time, and the mixture was heated to reflux for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain a crude product. The crude product was then subjected to column chromatography to obtain an organic electroluminescent material (151) (4.22 g, yield 67%), MS (EI): 752 (M+).
[0176] Example 14:
[0177]
[0178] The synthesis method of the organic electroluminescent material (278) is as follows:
[0179]
[0180] Compound 14-a (4 g, 402.24 g / mol, 9.97 mmol), compound 14-b (1.1 eq, 3.56 g, 324.18 g / mol, 10.97 mmol), and sodium carbonate (2 eq, 2.11 g, 105.99 g / mol, 19.95 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 14-a) and water (80 g, 20 times the mass of compound 14-a), stirred and mixed thoroughly, and then... Tris(o-tolyl)phosphine (5% eq, 0.15 g, 304.37 g / mol, 0.5 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.1 mmol) were added one-time, and the mixture was heated to reflux for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain a crude product. The crude product was then subjected to column chromatography to obtain an organic electroluminescent material (278) (4.83 g, yield 80.6%), MS (EI): 601 (M+).
[0181] Example 15:
[0182]
[0183] The synthesis method of the organic electroluminescent material (281) is as follows:
[0184]
[0185] Compound 15-a (4 g, 402.24 g / mol, 9.97 mmol), compound 15-b (1.1 eq, 3.56 g, 324.18 g / mol, 10.97 mmol), and sodium carbonate (2 eq, 2.11 g, 105.99 g / mol, 19.95 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 15-a) and water (80 g, 20 times the mass of compound 15-a), stirred and mixed thoroughly, and then... Tris(o-tolyl)phosphine (5% eq, 0.15 g, 304.37 g / mol, 0.5 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.1 mmol) were added one-time, and the mixture was heated to reflux for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain a crude product. The crude product was then subjected to column chromatography to obtain the organic electroluminescent material (281) (4.83 g, yield 80.5%), MS (EI): 601 (M+).
[0186] Example 16:
[0187]
[0188] The synthesis method of the organic electroluminescent material (287) is as follows:
[0189] S1:
[0190]
[0191] Compound 16-a (5 g, 317.76 g / mol, 15.89 mmol), compound 16-b (1.1 eq, 3.46 g, 198.03 g / mol, 17.47 mmol), and sodium carbonate (2 eq, 3.37 g, 105.99 g / mol, 31.77 mmol) were added to ethylene glycol diamine ether (100 g, 20 times the mass of compound 16-a) and water (100 g, 20 times the mass of compound 16-a), and the mixture was stirred. After homogenization, tris(o-tolyl)phosphine (5% eq, 0.24 g, 304.37 g / mol, 0.79 mmol) and palladium(II) acetate (1% eq, 0.04 g, 224.51 g / mol, 0.16 mmol) were added sequentially. The mixture was heated to reflux and reacted for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 16-c (5.01 g, yield 79.4%), MS (EI): 391 (M+).
[0192] S2:
[0193]
[0194] Compound 16-c (4.5 g, 391.06 g / mol, 11.57 mmol), compound 16-d (1.1 eq, 2.7 g, 212.01 g / mol, 12.73 mmol), and sodium carbonate (2 eq, 2.45 g, 105.99 g / mol, 23.14 mmol) were added to ethylene glycol diamine ether (90 g, 20 times the mass of compound 16-c) and water (90 g, 20 times the mass of compound 16-c), and the mixture was stirred until homogeneous. Then, tris(o-tolyl)phosphine (5% eq, 0.18 g, 304.37 g / mol, 0.58 mmol) and palladium(II) acetate (1% eq, 0.03 g, 224.51 g / mol, 0.12 mmol) were added sequentially. After the mixture was heated to reflux for 15 h, the organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 16-e (4.16 g, yield 75.1%), MS (EI): 478 (M+).
[0195] S3:
[0196]
[0197] Compound 16-e (4 g, 478.34 g / mol, 8.38 mmol), compound 16-f (1.1 eq, 2.99 g, 324.18 g / mol, 9.22 mmol), and sodium carbonate (2 eq, 1.78 g, 105.99 g / mol, 16.77 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 16-e) and water (80 g, 20 times the mass of compound 16-e), stirred and mixed thoroughly, and then added sequentially... Tris(o-tolyl)phosphine (5% eq, 0.13 g, 304.37 g / mol, 0.42 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.08 mmol) were added, and the mixture was heated to reflux for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain a crude product. The crude product was then subjected to column chromatography to obtain an organic electroluminescent material (287) (3.88 g, yield 68.3%), MS (EI): 677 (M+).
[0198] Example 17:
[0199]
[0200] The synthesis method of the organic electroluminescent material (289) is as follows:
[0201] S1:
[0202]
[0203] Compound 17-a (4.5 g, 391.06 g / mol, 11.57 mmol), compound 17-b (1.1 eq, 2.7 g, 212.01 g / mol, 12.73 mmol), and sodium carbonate (2 eq, 2.45 g, 105.99 g / mol, 23.14 mmol) were added to ethylene glycol diamine ether (90 g, 20 times the mass of compound 17-a) and water (90 g, 20 times the mass of compound 17-a), and the mixture was stirred until homogeneous. Then, tris(o-tolyl)phosphine (5% eq, 0.18 g, 304.37 g / mol, 0.58 mmol) and palladium(II) acetate (1% eq, 0.03 g, 224.51 g / mol, 0.12 mmol) were added sequentially. After the mixture was heated to reflux for 15 h, the organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 17-c (4.13 g, yield 74.7%), MS (EI): 478 (M+).
[0204] S2:
[0205]
[0206] Compound 17-c (4 g, 478.34 g / mol, 8.38 mmol), compound 17-d (1.1 eq, 2.99 g, 324.18 g / mol, 9.22 mmol), and sodium carbonate (2 eq, 1.78 g, 105.99 g / mol, 16.77 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 17-c) and water (80 g, 20 times the mass of compound 17-c), stirred and mixed thoroughly, and then added sequentially... Tris(o-tolyl)phosphine (5% eq, 0.13 g, 304.37 g / mol, 0.42 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.08 mmol) were added, and the mixture was heated to reflux for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain a crude product. The crude product was then subjected to column chromatography to obtain an organic electroluminescent material (289) (3.95 g, yield 69.5%), MS (EI): 677 (M+).
[0207] Example 18:
[0208]
[0209] The synthesis method of organic electroluminescent material (293) is as follows:
[0210] S1:
[0211]
[0212] Compound 18-a (5 g, 317.76 g / mol, 15.89 mmol), compound 18-b (1.1 eq, 3.88 g, 222.05 g / mol, 17.47 mmol), and sodium carbonate (2 eq, 3.37 g, 105.99 g / mol, 31.77 mmol) were added to ethylene glycol diamine ether (100 g, 20 times the mass of compound 18-a) and water (100 g, 20 times the mass of compound 18-a), and the mixture was stirred. After homogenization, tris(o-tolyl)phosphine (5% eq, 0.24 g, 304.37 g / mol, 0.79 mmol) and palladium(II) acetate (1% eq, 0.04 g, 224.51 g / mol, 0.16 mmol) were added sequentially. The mixture was heated to reflux and reacted for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 18-c (5.19 g, yield 78.7%), MS (EI): 415 (M+).
[0213] S2:
[0214]
[0215] Compound 18-c (4.5 g, 415.08 g / mol, 10.84 mmol), compound 18-d (1.1 eq, 2.53 g, 212.01 g / mol, 11.93 mmol), and sodium carbonate (2 eq, 2.30 g, 105.99 g / mol, 21.68 mmol) were added to ethylene glycol diamine ether (90 g, 20 times the mass of compound 18-c) and water (90 g, 20 times the mass of compound 18-c), and the mixture was stirred. After homogenization, tris(o-tolyl)phosphine (5% eq, 0.16 g, 304.37 g / mol, 0.54 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.11 mmol) were added sequentially. The mixture was heated to reflux and reacted for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 18-e (3.53 g, yield 76.8%), MS (EI): 423 (M+).
[0216] S3:
[0217]
[0218] Compound 18-e (3 g, 423.46 g / mol, 7.08 mmol), compound 18-f (1.1 eq, 2.53 g, 324.18 g / mol, 7.79 mmol), and sodium carbonate (2 eq, 1.50 g, 105.99 g / mol, 114.16 mmol) were added to ethylene glycol diamine ether (60 g, 20 times the mass of compound 18-e) and water (60 g, 20 times the mass of compound 18-e), stirred and mixed thoroughly, and then added sequentially... Tris(o-tolyl)phosphine (5% eq, 0.11 g, 304.37 g / mol, 0.35 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.07 mmol) were added, and the mixture was heated to reflux for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain a crude product. The crude product was then subjected to column chromatography to obtain an organic electroluminescent material (293) (3.34 g, yield 67.2%), MS (EI): 701 (M+).
[0219] Example 19:
[0220]
[0221] The synthesis method of the organic electroluminescent material (297) is as follows:
[0222] S1:
[0223]
[0224] Compound 19-a (5.05 g, 317.76 g / mol, 15.89 mmol), compound 19-b (2.2 eq, 4.26 g, 121.93 g / mol, 34.96 mmol), and sodium carbonate (4 eq, 6.74 g, 105.99 g / mol, 63.56 mmol) were added to ethylene glycol diamine ether (150 g, 30 times the mass of compound 19-a) and water (150 g, 30 times the mass of compound 19-a), and stirred. After mixing, tris(o-tolyl)phosphine (10% eq, 0.48 g, 304.37 g / mol, 1.59 mmol) and palladium(II) acetate (2% eq, 0.07 g, 224.51 g / mol, 0.32 mmol) were added sequentially. The mixture was heated to reflux and reacted for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain the crude product. The crude product was then subjected to column chromatography to obtain compound 19-c (6.39 g, yield 81.7%), MS (EI): 492 (M+).
[0225] S2:
[0226]
[0227] Compound 19-c (4 g, 492.32 g / mol, 8.12 mmol), compound 19-d (1.1 eq, 3.12 g, 349.19 g / mol, 8.94 mmol), and sodium carbonate (2 eq, 1.72 g, 105.99 g / mol, 16.24 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 19-c) and water (80 g, 20 times the mass of compound 19-c), stirred and mixed thoroughly, and then added sequentially... Tris(o-tolyl)phosphine (5% eq, 0.12 g, 304.37 g / mol, 0.41 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.1 mmol) were added, and the mixture was heated to reflux for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain a crude product. The crude product was then subjected to column chromatography to obtain an organic electroluminescent material (297) (4.39 g, yield 75.4%), MS (EI): 716 (M+).
[0228] Example 20:
[0229]
[0230] The synthesis method of organic electroluminescent material (301) is as follows:
[0231]
[0232] Compound 20-a (4 g, 492.32 g / mol, 8.12 mmol), compound 20-b (1.1 eq, 2.90 g, 324.18 g / mol, 8.94 mmol), and sodium carbonate (2 eq, 1.72 g, 105.99 g / mol, 16.24 mmol) were added to ethylene glycol diamine ether (80 g, 20 times the mass of compound 20-a) and water (80 g, 20 times the mass of compound 20-b), stirred and mixed thoroughly, and then added sequentially... Tris(o-tolyl)phosphine (5% eq, 0.12 g, 304.37 g / mol, 0.41 mmol) and palladium(II) acetate (1% eq, 0.02 g, 224.51 g / mol, 0.1 mmol) were added, and the mixture was heated to reflux for 15 h. The organic phase was separated, washed with water, and concentrated under reduced pressure to obtain a crude product. The crude product was then subjected to column chromatography to obtain an organic electroluminescent material (301) (4.15 g, yield 73.8%), MS (EI): 691 (M+).
[0233] The triplet energy levels T1, thermogravimetric temperatures Td, and highest occupied molecular orbital (HOMO) energy levels of ETL-1 and the organic electroluminescent materials 1, 2, 5, 11, 13, 17, 36, 53, 73, 97, 121, 126, 151, 278, 281, 287, 289, 293, 297, and 301 of this invention were tested and calculated.
[0234] Note: The triplet energy level T1 was measured by a 3V EDX8300H vacuum spectrometer; the thermogravimetric temperature Td was the temperature at which 5% weight loss occurred in a nitrogen atmosphere, measured on a TGA N-1000 thermogravimetric analyzer with a nitrogen flow rate of 10 mL / min; the highest occupied molecular orbital (HOMO) energy level was measured by an ionization energy testing system (IPS4).
[0235]
[0236] Table 1:
[0237]
[0238]
[0239] As shown in Table 1 above, the organic electroluminescent material of the present invention has a high thermal weight loss temperature, high thermal stability, and long device lifespan; the high triplet energy level can block energy loss of the light-emitting layer, thereby improving the luminous efficiency of the device; and the appropriate HOMO energy level can solve the carrier injection problem, thereby reducing the device voltage.
[0240] Performance testing:
[0241] Application Example 1:
[0242] ITO was used as the anode substrate material for the reflective layer, and its surface was treated sequentially with water, acetone, and N2 ions.
[0243] A hole injection layer (HIL) with a thickness of 10 nm is deposited on top of the ITO anode substrate.
[0244] A hole transport layer (HTL) with a thickness of 120 nm is formed by depositing an NPD on top of the hole injection layer (HIL);
[0245] 9,10-Bis(2-naphthyl)anthraces (ADN) was used as the main blue light source material and BD-1 was used as the blue light dopant material (the amount of BD-1 was 5% of the weight of ADN). The two materials were evaporated at different rates on the hole transport layer (HTL) to form a light-emitting layer with a thickness of 20 nm.
[0246] The organic electroluminescent material (1) of the present invention is deposited onto the light-emitting layer to obtain an electron transport layer (ETL) with a thickness of 35 nm. An electron injection layer (EIL) with a thickness of 2 nm is deposited on top of the electron transport layer (ETL).
[0247] Subsequently, magnesium (Mg) and silver (Ag) were mixed in a 9:1 ratio and vapor-deposited to obtain a cathode with a thickness of 15 nm. A DNTPD with a thickness of 65 nm was deposited on the cathode sealing layer. In addition, the cathode surface was sealed with a UV-curable adhesive and a sealing cap containing a desiccant to protect the organic electroluminescent device from the influence of oxygen or moisture in the atmosphere. Thus, an organic electroluminescent device was prepared.
[0248]
[0249] Application Example 2-20
[0250] Organic electroluminescent materials 2, 5, 11, 13, 17, 36, 53, 73, 97, 121, 126, 151, 278, 281, 287, 289, 293, 297, and 301 from Examples 2-18 of the present invention were used as electron transport layers (ETLs), with the other parts being the same as in Application Example 1. Based on this, organic electroluminescent devices of Application Examples 2-20 were fabricated.
[0251] Comparison Example
[0252] The difference from Application Example 1 is that ETL-1 is used as the electron transport layer (ETL), otherwise it is the same as Application Example 1.
[0253] The organic electroluminescent device manufactured in the above application example and the organic electroluminescent device manufactured in the comparative example have the characteristic of operating at a current density of 10 mA / cm².2 The results were measured under the specified conditions and are shown in Table 2.
[0254] Table 2:
[0255]
[0256]
[0257] As shown in Table 2 above, the experimental comparison data reveals that the organic electroluminescent device prepared using the organic electroluminescent material of this invention exhibits a significantly lower voltage and a significantly higher luminous efficiency compared to the control example. This demonstrates that the organic electroluminescent material of this invention can greatly reduce the driving voltage of the device, thereby significantly reducing power consumption and significantly improving luminous efficiency. Furthermore, by reducing the driving voltage, the lifetime of the organic electroluminescent device is significantly improved.
Claims
1. An organic electroluminescent device, characterized in that, The organic electroluminescent device comprises an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode stacked sequentially; the electron transport layer contains an organic electroluminescent material as shown in formula (97) or formula (297); 。 2. An organic electroluminescent display device, characterized in that, It contains the organic electroluminescent device as described in claim 1.
3. An organic electroluminescent lighting device, characterized in that, It contains the organic electroluminescent device as described in claim 1.